U.S. patent number 8,317,975 [Application Number 11/412,593] was granted by the patent office on 2012-11-27 for product and processes from an integrated forest biorefinery.
This patent grant is currently assigned to The Research Foundation of the State University of New York. Invention is credited to Thomas E. Amidon, Jeremy Bartholomew, Raymond Francis, Bandaru V. Ramarao, Gary M. Scott, Christopher D. Wood.
United States Patent |
8,317,975 |
Amidon , et al. |
November 27, 2012 |
Product and processes from an integrated forest biorefinery
Abstract
An omnibus process of pulping and bleaching lignocellulosic
materials in which a charge of a lignocellulosic material is
biopulped and/or water extracted prior to pulping and bleaching.
The lignocellulosic material may be mechanically pulped and
bleached in the presence of an enzyme that breaks
lignin-carbohydrate complexes. The aqueous extract in embodiments
including a water extract step is separated into acetic acid and
hemicellulose sugar aqueous solutions.
Inventors: |
Amidon; Thomas E. (Jamesville,
NY), Francis; Raymond (Syracuse, NY), Scott; Gary M.
(Syracuse, NY), Bartholomew; Jeremy (Pluttsburgh, NY),
Ramarao; Bandaru V. (Fayetteville, NY), Wood; Christopher
D. (Syracuse, NY) |
Assignee: |
The Research Foundation of the
State University of New York (Albany, NY)
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Family
ID: |
37910156 |
Appl.
No.: |
11/412,593 |
Filed: |
April 27, 2006 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20070079944 A1 |
Apr 12, 2007 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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PCT/US2005/013216 |
Apr 20, 2005 |
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60563837 |
Apr 20, 2004 |
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60679151 |
May 9, 2005 |
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Current U.S.
Class: |
162/14; 162/29;
162/19; 162/67; 162/65; 162/55; 162/43; 162/72; 162/52; 162/82;
162/87; 162/70; 162/78 |
Current CPC
Class: |
D21C
1/02 (20130101); D21H 11/10 (20130101); D21C
9/147 (20130101); D21C 11/0007 (20130101); D21H
11/08 (20130101); D21C 9/163 (20130101); D21C
3/222 (20130101); D21C 9/123 (20130101); D21C
9/1063 (20130101); D21C 3/02 (20130101); D21H
11/02 (20130101); D21C 3/04 (20130101); D21H
17/005 (20130101); D21H 21/32 (20130101); D21C
3/00 (20130101); D21C 5/005 (20130101); D21C
9/1057 (20130101) |
Current International
Class: |
D21C
3/26 (20060101); D21C 3/02 (20060101); D21C
9/14 (20060101); D21C 9/147 (20060101); D21C
9/10 (20060101); D21C 9/153 (20060101) |
Field of
Search: |
;162/14,17,19,24,26,29,30.11,41-43,47,52,55,63-67,70,78,81,72,82,87 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1340121 |
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Mar 2002 |
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CN |
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WO 0047812 |
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Aug 2000 |
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WO |
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WO 03/046227 |
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Jun 2003 |
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WO |
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WO 2005103370 |
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Nov 2005 |
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WO |
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WO 2006121634 |
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Nov 2006 |
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WO |
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Other References
A Kaye, "New digester additives help to optimize kraft pulp mills,"
Ma y, 2004, Nalco Company, pp. 1-2. cited by examiner .
E. Line Springer, " Prehydroysis of Hardwoods with Dilute Sulfuric
Acid," 1985, American Chemical Society, pp. 614-623. cited by
examiner .
Sven A. Rydholm, "Pulping Processes," 1965, Interscience
Publishers, pp. 663-671. cited by examiner .
Garrote et al., "Hydrothermal processing of lignocellulosic
materials," Holz als Roh- und Werkstoff vol. 57, 1999 pp. 191-202.
cited by examiner .
Parajo et al., "Production of xylooligo-saccharides by
autohydrolysis of lignocellulosic materials," 2004, Trends in Food
Science & Technology, pp. 115-120. cited by examiner .
Conner et al., "Kinetic Modelling of Hardwood Prehydrolysis. Part
III. Water and dilute Acetic acid Prehydrolysis of Southern red
Oak," 1986, Wood and Fiber Science, vol. 18(2), pp. 248-263. cited
by examiner .
Gullichsen et al., Chemical Pulping, Book 6A, Papermaking Science
and Technology, Fapet Oy, 1999, pp. A411-A416, pp. A520-A521, and
pp. A559. cited by other .
Smook, Handbook for Pulp and Paper Technologists, Angus Wilde
Publications Inc., 2.sup.nd edition, 1992, pp. 61 and 77. cited by
other .
Li Hanquan, Studies on Biological Pulping and Biological Bleaching
Techniques in the Paper-Making Industry, Journal of Jiujiang
Teacher's College, No. 6, p. 20-24, 2003. cited by other .
CN Office Action dated Jan. 15, 2010 with English translation.
cited by other.
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Primary Examiner: Fortuna; Jose A
Attorney, Agent or Firm: Scully, Scott, Murphy &
Presser, P.C.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of International Application No.
PCT/US2005/013216 filed Apr. 20, 2005, which claims benefit from
U.S. provisional patent application, Ser. No. 60/563,837, filed
Apr. 20, 2004. This application also claims benefit from U.S.
provisional application, Ser. No. 60/679,151, filed May 9, 2005.
Claims
What is claimed is:
1. A process of pulping lignocellulosic materials consisting of the
steps of: (a) contacting a charge of a lignocellulosic material
with water, the lignocellulosic material containing an initial
amount of xylan, the water and charge of lignocellulosic material
maintained at a temperature in the range of between about
20.degree. C. and about 200.degree. C. and lowering the pH to
between about 3.0 and about 6.9 by producing acetic acid from the
reaction of the water and lignocellulosic material for a period of
about 90 minutes to about 120 minutes, wherein an aqueous extract
and extracted lignocellulosic materials are obtained, the aqueous
extract containing about 65% of the initial amount of xylan present
in the charge of lignocellulosic material; (b) pulping a portion of
said extracted lignocellulosic materials wherein individual fibers
and fiber bundles are produced and have a kappa number of at least
7 in less than 150 minutes; and (c) bleaching said product of said
step (b).
2. The process in accordance with claim 1 wherein said aqueous
extract of said step (a) is recovered.
3. The process in accordance with claim 2 comprising separating
said aqueous extract into an aqueous acetic acid solution and an
aqueous hemicellulose sugar solution.
4. The process in accordance with claim 3 wherein said separation
of said aqueous extract occurs by molecular separation.
5. The process in accordance with claim 4 wherein said molecular
separation occurs by flowing said aqueous extract across a
nano-sized porous membrane.
6. The process in accordance with claim 1 wherein said pulping step
(b) is effectuated by a process selected from the group consisting
of mechanical pulping, chemical pulping and a combination of
mechanical and chemical pulping.
7. The process in accordance with claim 6 wherein said pulping step
(c) is effectuated by chemical pulping.
8. The process in accordance with claim 7 wherein said chemical
pulping is effectuated by kraft cooking.
9. The process in accordance with claim 7 wherein said chemical
pulping is effectuated by kraft/polysulfide cooking.
10. The process in accordance with claim 7 wherein said chemical
pulping is effectuated by kraft cooking in the presence of an
anthraquinone.
11. The process in accordance with claim 7 wherein said chemical
pulping is effectuated by soda cooking.
12. The process in accordance with claim 7 wherein said chemical
pulping is effectuated by soda cooking in the presence of a redox
catalyst.
13. The process in accordance with claim 7 wherein said chemical
pulping is effectuated by soda cooking catalyzed by an
anthraquinone.
14. The process in accordance with claim 7 wherein said chemical
pulping is conducted in the presence of a base selected from the
group consisting of potassium hydroxide, calcium hydroxide and
magnesium hydroxide.
15. The process in accordance with claim 7 wherein said chemical
pulping is conducted in the presence of an anion selected from the
group consisting of a carbonate, bicarbonate, sulfite, bisulfite
and mixtures thereof.
16. The process in accordance with claim 7 wherein said bleaching
step (c) is effectuated by contacting said pulp product of said
step (c) with an oxidizing agent selected from the group consisting
of oxygen, hydrogen peroxide, ozone, peracetic acid, chlorine,
chlorine dioxide, a hypochlorite anion and mixtures thereof.
17. The process in accordance with claim 16 wherein said bleaching
step (c) comprises contacting said pulp with chlorine dioxide in
the presence of oxygen.
18. The process in accordance with claim 16 wherein said bleaching
step (c) comprises contacting said pulp with chlorine dioxide in
the presence of magnesium hydroxide or another magnesium-containing
compound.
19. The process in accordance with claim 16 wherein said bleaching
step (c) comprises contacting said pulp with chlorine dioxide in
the presence of oxygen and magnesium hydroxide or another
magnesium-containing compound.
20. The process in accordance with claim 16 wherein said bleaching
step (c) comprises contacting said pulp with chlorine dioxide in
the presence of potassium hydroxide or calcium hydroxide.
21. The process in accordance with claim 6 wherein said pulping
step (c) is effectuated by a combination of mechanical and chemical
pulping.
22. The process in accordance with claim 21 wherein said
combination of mechanical and chemical pulping is effectuated by
chemical pulping and fiber separation by mechanical force.
23. The process in accordance with claim 22 wherein said chemical
pulping is effectuated by kraft cooking.
24. The process in accordance with claim 22 wherein said chemical
pulping is effectuated by kraft/polysulfide cooking.
25. The process in accordance with claim 22 wherein said chemical
pulping is effectuated by kraft cooking in the presence of an
anthraquinone.
26. The process in accordance with claim 22 wherein said chemical
pulping is effectuated by soda cooking.
27. The process in accordance with claim 22 wherein said chemical
pulping is effectuated by soda cooking in the presence of a redox
catalyst.
28. The process in accordance with claim 22 wherein said chemical
pulping is effectuated by soda cooking in the presence of an
anthraquinone catalyst.
29. The process in accordance with claim 22 wherein said chemical
pulping is effectuated in the presence of a base selected from the
group consisting of potassium hydroxide, calcium hydroxide and
magnesium hydroxide.
30. The process in accordance with claim 22 wherein said chemical
pulping is effectuated in the presence of an anion selected from
the group consisting of a carbonate, bicarbonate, sulfite,
bisulfate and mixtures thereof.
31. The process in accordance with claim 21 wherein said bleaching
step (c) is effectuated by contacting said pulp product of said
step (b) with an oxidizing agent selected from the group consisting
of oxygen, hydrogen peroxide, ozone, peracitic acid, chlorine,
chlorine dioxide, a hypochlorite anion and mixtures thereof.
32. The process in accordance with claim 31 wherein said pulp is
bleached in two oxygen-contacting stages.
33. The process in accordance with claim 32 wherein pulp washing
step occurs between said two oxygen-contacting stages.
34. The process in accordance with claim 32 wherein said pulp is
contacted with oxygen- and sodium hydroxide between said oxygen
contacting stages.
35. The process in accordance with claim 31 wherein said bleaching
step (c) comprises contacting said pulp with chlorine dioxide in
the presence of oxygen.
36. The process in accordance with claim 31 wherein said bleaching
step (c) comprises contacting said pulp with chlorine dioxide in
the presence of magnesium hydroxide or another magnesium-containing
compound.
37. The process in accordance with claim 31 wherein said bleaching
step (c) comprises contacting said pulp with chlorine dioxide in
the presence of oxygen and magnesium hydroxide or another
magnesium-containing compound.
38. The process in accordance with claim 31 wherein said bleaching
step (c) comprises contacting said pulp with chlorine dioxide in
the presence of potassium or calcium hydroxide.
39. The process in accordance with claim 6 wherein said pulping
step (b) is effectuated by mechanical pulping.
40. The process in accordance with claim 39 wherein said bleaching
step (c) is effectuated by contacting said pulp product of step (b)
with hydrogen peroxide.
Description
BACKGROUND OF THE INVENTION
1. Field of Invention
The invention relates generally to the field of pulping and
bleaching lignocellulosic materials. More specifically, the present
invention is directed to pulping and bleaching of lignocellulosic
materials which includes biopulping and/or water extraction
processes.
2. Description of the Prior Art
There are a number of processes that convert lignocellulosic
materials to pulp. Pulp is the fibrous slurry that is fed to a
paper machine to produce paper. Mechanical, chemical and hybrid
methods dominate commercial pulping plants. About 25% of worldwide
pulp production is mechanical pulp. It is a high-yield process but
suffers from high energy costs and damage to the lignocellulosic
fibers. This damage produces lower strength paper. These
disadvantages (cost and quality) limit the number of applications
for pulp.
Chemical pulp is the pulp produced by chemical pulping. The
dominant chemical wood pulping process is the kraft process. In
this process a digesting solution of sodium hydroxide and sodium
sulfide is employed. The advantage of chemical pulp is reduced
damage to the lignocellulosic fibers insofar as the chemical
pulping operation permits a sufficient amount of the lignin
constituent in the lignocellulosic materials to be dissolved so
that the lignocellulosic fibers separate without significant
mechanical action.
Recently, a means for improving pulping has been developed. That
new development is the addition of a biopulping step. The
production of pulp begins with lignocellulosic materials, such as
wood chips. When a biopulping step is used, the lignocellulosic
materials are `digested` with one or more fungi types prior to
mechanical or chemical pulping. The fungi soften the
lignocellulosic materials by degrading or breaking
lignin-carbohydrate complexes in the lignocellulosic materials.
A process that describes bioprocessing in detail is U.S. Pat. No.
6,402,887 whose disclosure is incorporated herein by reference.
That patent describes a process of biopulping of industrial wood
waste using fungi which selectively degrade lignin.
After biopulping, the wood chips are mechanically or chemically
pulped into individual fibers. The fungi and the produced enzymes
are destroyed during the thermomechanical pulping process. Due, in
large part, to the biochemical action of the fungi, less energy is
required to convert the chips to fibers. Some investigators claim
energy savings of at least 30%. The easier conversion from chip to
fiber means less damage to the fibers. The paper formed from these
fibers is stronger.
Although a biopulping step reduces the energy costs associated with
pulping, it does not address the absence of recovery of the full
commercial value of lignocellulosic materials. Lignocellulosic
materials comprise cellulose, lignin and hemicellulose.
Conventional pulping operations recover the cellulose values in the
form of fibers. The value provided by lignin, which is removed in
the pulping operation, is recovered as energy, by its
combustion.
That is, conventional pulping, whether or not including a
biopulping step, does not address a major aspect of commercial
exploitation of lignocellulosic materials. As stated above, there
are three major components in lignocellulosic materials. The first
is cellulose. The pulping operation yields fibers which are
substantially the cellulose component. A second component is
lignin, which is removed in the pulping operation. Indeed,
biopulping involves fungal digestion of lignin. The third
component, which is usually utilized for its energy value, along
with the lignin, is hemicellulose.
Hemicellulose is a mixture of sugar and sugar acids, a major
component of which are xylans. The difficulty in the prior art of
isolating the product values of hemicellulose has limited the
utility of the hemicellulose component in wood to the marginal
energy value of that component. An acid pretreatment can be used to
depolymerize the xylan to xylose and xylose oligomers. The acid
would also catalyzes hydrolysis of acetyl groups (2-4.5% of the
weight of the original wood) to acetic acid. If the wood is treated
with hot water a low initial rate of acetic acid would be obtained.
However, each acetic acid molecule formed would then act as an acid
catalyst in a process referred to as autohydrolysis.
Additionally, there are some drawbacks to biopulping, such as a
reduction in the brightness and opacity of the resulting fibers.
Since the production of higher quality papers is desirable, use of
biopulped fibers will require improvements in brightness and
opacity. Research is underway to develop strategies to address
these drawbacks. Preliminary bleaching studies with hydrogen
peroxide and addition of calcium carbonate to improve both
brightness and opacity have met with early success.
The present invention provides a method for producing pulp that
addresses the above and other issues.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed to an omnibus process of pulping
lignocellulosic materials, especially wood chips, wherein many of
the problems of both mechanical and chemical pulping in terms of
pulping efficiency, production of quality paper and recovery of
chemical values, is optimized.
In accordance with the present invention a process of pulping
lignocellulosic materials is provided. In one aspect of the present
invention lignocellulosic materials are treated with a fungus that
breaks lignin-carbohydrate complexes. The lignocellulosic materials
product of this contact is thereupon mechanically, chemically or
mechanically-chemically pulped. The pulp product of this step is
bleached. That bleaching step occurs in the presence of an enzyme
which breaks lignin-carbohydrate complexes. In a preferred
embodiment that enzyme is the crude broth product of the fungus
contacting step. The lignocellulosic materials product that is not
pulped and the pulp which is not bleached is combusted.
In another aspect of pulping lignocellulosic materials in
accordance with the present invention lignocellulosic materials,
whether or not contacted with a fungus that breaks
lignin-carbohydrate complexes, is contacted with hot water at a
temperature in the range of between about 20.degree. C. and about
200.degree. C. and a pH in the range of between about 0.5 and about
6.9 for a period in the range of between about 1 minute and about 7
days. The product of this extraction is an aqueous extract and
extracted lignocellulosic materials. The extracted lignocellulosic
materials are pulped and subsequently bleached. The extracted
lignocellulosic materials not subject to pulping is combusted.
In yet another aspect of the process of pulping lignocellulosic
materials of the present invention a charge of a lignocellulosic
material is contacted with a fungus which breaks
lignin-carbohydrate complexes in lignocellulosic materials. The
lignocellulosic material product of this contact is contacted with
water at a temperature in the range of between about 20.degree. C.
and about 200.degree. C. and a pH in the range of between 0.5 and
about 6.9 for a period of time in the range of between about 1
minute and about 7 days wherein an aqueous extract and the
extracted lignocellulosic material product is obtained. The
extracted lignocellulosic material product is pulped wherein
individual fibers and fiber bundles are produced. The pulp product
of this step is bleached. Finally, the extracted lignocellulosic
product not subjected to pulping and bleaching is combusted.
In still another aspect of the process of pulping lignocellulosic
materials of the present invention a charge of lignocellulosic
material is pulped wherein individual fibers and fiber bundles are
produced. The pulped product is thereupon bleached by contacting
the pulped product with chlorine dioxide in the presence of an
agent selected from the group consisting of oxygen, magnesium
hydroxide, another magnesium-containing compound, oxygen and
magnesium hydroxide or another magnesium-containing compound,
potassium hydroxide and calcium hydroxide. Finally, in another
aspect of the present invention, a pulp, produced in accordance
with the process of pulping lignocellulosic materials, is provided.
The pulp has a specific surface area in the range of between about
5,000 cm.sup.2/g and about 40,000 cm.sup.2/g and a specific volume
in the range of between about 1.5 cm.sup.3/g and about 4.0
cm.sup.3/g.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be better understood by reference to the
following drawings of which:
FIG. 1 illustrates the lignolytic enzyme activity change for the
laccase enzyme, where thermomechanical pulping (TMP) is performed
over a six hour treatment time on Picea abies (Norway Spruce) wood
chips with fungal treatment using P. subserialis, T. versicolor and
C. subvermispora, in accordance with Example 1.
FIG. 2 illustrates the lignolytic enzyme activity change for the
manganese peroxidase enzyme, for comparison with the results of
FIG. 1 in Example 1.
FIG. 3 is a schematic flow diagram of the omnibus pulping process
of the present application;
FIG. 4 is a graph demonstrating yield as a function of Kappa number
in Example 2;
FIG. 5 is a graph demonstrating viscosity as a function of Kappa
number in Example 2;
FIG. 6 is a graph showing delignification as a function of kraft
cooking times in Example 2;
FIG. 7 is a graph demonstrating void volume of wood chips as a
function of the temperatures of hot water extraction in Example
2;
FIG. 8 is an .sup.1H-NMP spectra recorded at 600 MHz for 5 sugars
and the internal standard in Example 3;
FIG. 9 is a graph demonstrating lignin remaining in wood following
extraction as fraction of the original wood mass in Example 3;
FIG. 10 is a graph showing glucose present as a function of hot
water extraction temperature in Example 3;
FIG. 11 is a graph showing maximum xylan recovery as a function of
hot water extraction temperature in Example 3.
FIG. 12 is a plot of xylan solubilization for sugar maple wood meal
(i) and wood chips (ii) in Example 5;
FIG. 13 is a plot xylan deacetylation for sugar maple wood meal (i)
and wood chips (ii) in Example 5;
FIG. 14 is a plot showing the concentration of acetyl groups in the
hydrolyzate with increasing severity in Example 5;
FIG. 15 is a plot showing pH of hydrolyzate as a function of
treatment severity in Example 5;
FIG. 16 is a plot showing xylose yield as a function of treatment
severity in Example 5; and
FIG. 17 is a plot showing the formation of furfural as a function
of treatment severity in Example 5.
DETAILED DESCRIPTION OF THE INVENTION
The pulping process of the present invention begins with the raw
material utilized in the production of pulp and its
by-products--lignocellulosic materials. The lignocellulosic
materials utilized in pulping are woods, grasses and the like. The
classes of wood within this category include wood chips or tree
species especially useful as a biomass fuel, e.g., a shrub willow
(Salix dasyclados) and the like. In general, woods not suitable for
use as lumber and certain species of grass are most commonly
employed as raw materials in pulp and subsequent paper
production.
Lignocellulosic materials, denoted at 1, in accordance with the
omnibus process depicted in FIG. 3, is, in one preferred
embodiment, subjected to hot water contact 3. In this step, water,
at temperature in the range of between about 20.degree. C. and
about 200.degree. C. and a pH in the range of between about 0.5 and
about 6.9 contacts a charge of the lignocellulosic material for a
period in the range of between about 1 minute and about 7 days.
More preferably, the water is at a temperature is in the range of
between about 100.degree. C. and about 160.degree. C., at a pH is
the range of between about 2.0 and about 5.0 and a contact time
between the lignocellulosic material charge and the hot water in
the range of between about 10 minutes and about 4 days.
This contacting step, which serves as an extraction step,
represents a significant advance in the art insofar as this step
not only enhances the rate of pulping, which is conducted
subsequent to this step, but, in addition, the step that occurs
downstream of the pulping step, pulp bleaching, is more successful.
That is, the bleaching step of the present invention yields a pulp
having greater brightness than the pulp prepared from the same
lignocellulosic material not subjected to the hot water extraction
of the present process. It is furthermore theorized that the
carbohydrate/cellulose of the brighter pulp, resulting from the
step, has a higher average degree of polymerization which results
in paper and paperboard products having higher strength properties
than similar products produced from pulp not subjected to hot water
extraction.
In regard to the rate of pulping, it is found that the rate of
pulping is increased by between about 1.2 and about 12 times than
an identical pulping step in which the same lignocellulosic
materials are not subjected to this hot water extraction step.
The hot water contacting step 3 produces an extracted
lignocellulosic product and an aqueous extract. The extract 13, an
aqueous solution, is subject to further processing to recover
chemical values present in the original lignocellulosic materials
charged into the process. The aqueous extract 13, in accordance
with this aim, is passed into a separation unit 14. In a
particularly preferred embodiment molecular separation is employed
to effectuate this result. Specifically, a molecular separation
occurs, preferably employing a mono-sized porous membrane, which
effects separation of hemicellulose sugars and acetic acid,
extracted from the lignocellulosic materials charge, present in the
aqueous extract 13.
This separation permits recovery of material values inherent in
lignocellulosic materials. Acetic acid is a highly prized commodity
chemical. Hemicellulose sugars, principally xylans, can, in the
absence of the separated acetic acid, be fermented to produce
ethanol and other valuable fermentation products. Xylans can also
be polymerized to produce important xylan polymers.
As depicted in FIG. 3, the aqueous extract 13 is separated by
molecular separation 14 into an acetic acid stream, accumulated at
15 and a hemicellulose sugar aqueous solution stream collected at
16. The hemicellulose sugar can, in the absence of acetic acid, be
fermented to produce ethanol and other commercially valuable
fermentation products. Ethanol and other fermentation products are
illustrated by reference numeral 17. Alternatively, the xylan sugar
16 can be polymerized to product xylan polymers 18.
The lignocellulosic material after hot water extraction is next
subjected to pulping. Pulping is effectuated by chemical pulping,
mechanical pulping or a combination of mechanical and chemical
pulping. Mechanical pulping, denoted by reference numeral 7, is
effectuated by methods known in the art. Usually, mechanical
pulping involves grinding the lignocellulosic materials on a
pulpstone refiner, e.g. a rotating disk attrition mill.
Chemical pulping, denoted by reference numeral 8, may be utilized
in the pulping step. A predominant chemical pulping method is the
kraft process. In the kraft process an alkaline pulping liquor or
digesting solution includes sodium hydroxide and sodium sulfide. In
a preferred embodiment the two components are present in a weight
ratio of about 3:1, sodium hydroxide to sodium sulfide.
In another preferred embodiment chemical pulping is effectuated by
a kraft process modification. That is, the kraft process is
modified by the addition of polysulfide which are introduced under
alkaline conditions and relatively low temperature, e.g. about
100.degree. C. to about 120.degree. C.
Another modification of the kraft process that may utilized in the
chemical pulping process is the addition of an anthraquinone. In a
preferred embodiment of this process, kraft cooking in the presence
of an anthraquinone, for example, sodium anthraquinone-2-sulfonate,
is added to the sodium hydroxide solution. In another embodiment of
this process small amounts of a quinone salt are added to kraft
pulping liquors.
Yet another chemical pulping process within the contemplation of
the present invention is soda cooking. In the soda cooking process
the lignocellulosic materials are contacted with sodium hydroxide.
Such a process is advantageously employed when the lignocellulosic
material is certain hardwood species or is a nonwood plant.
A related process that is encompassed by the chemical pulping step
of the present invention is the use of the soda cooking method
catalyzed by an anthraquinone.
A further related process favorably utilized in the process of the
present invention is soda cooking in the presence of a redox
catalyst. A preferred redox catalyst utilized in this embodiment is
anthraquinone (AQ) or 2-methylanthraquinone (MAQ). Kraft pulping is
the dominant process for the conversion of wood chips into pulp
fibers in the United States (.about.85% of all virgin pulps from
wood chips). The key to the kraft process is the Tomlinson furnace
that is quite efficient at recovering the pulping chemicals, NaOH
and Na.sub.2S. However, energy efficiency is becoming more
important each passing year and there is a sense of inevitability
that gasification of the black liquor (BL) will replace the
Tomlinson furnace for chemical and energy recovery. The current
estimates are that an optimized Tomlinson furnace would net
.about.900 kWh/ton of pulp while a gasifier would net around 2,200
kWh/ton of pulp. Gasification would allow a mill to generate more
thermal energy and also more electricity via turbines or
micro-turbines. Also, low quality biomass (LQB) could be mixed into
the BL to generate even more energy.
A major sulfur related problem is that the regeneration of
Na.sub.2S from kraft BL would be tedious for all gasification
processes. Some of the sulfur in the BL will be converted to
H.sub.2S in the fuel gases (Eqn. [1]). This H.sub.2S has to be
selectively removed by adsorption onto a solid sorbent or into a
solvent. The H.sub.2S would have to be desorbed from the solid
sorbent and the surface reconditioned for another sulfidation
cycle. If the H.sub.2S is absorbed into a solvent then desorption
into a non-reactive gas followed by re-absorption into NaOH or
Na.sub.2CO.sub.3 would be required. Poor efficiency and selectivity
was observed when direct absorption into caustic was attempted at
the New Bern mill where pilot scale gasification of kraft BL is
being attempted.
Na.sub.2S+CO.sub.2+H.sub.2O.fwdarw.H.sub.2S+Na.sub.2CO.sub.3
[1]
The chemicals in the soda/AQ process would be NaOH or KOH plus
0.05-0.1% AQ on chips. The small amount of residual AQ can be sent
to a gasifier since it is composed of carbon, hydrogen and oxygen
only.
Yet another chemical pulping process utilized in the present
invention is chemical pulping conducted in the presence of an anion
selected from the group consisting of a carbonate, bicarbonate,
sulfite, bisulfite and mixtures thereof. In this process sodium
carbonate is presently used to delignify wood to .about.85% yield
in semi-chemical pulping operations, i.e. a hybrid process between
chemical and mechanical pulping. Chemicals pulps are also produced
by sulfite and bisulfite cooking processes and carbonate and
bicarbonate anions are used for pH adjustment.
In still another method of the chemical pulping step of the process
of the present invention, chemical pulping, is conducted in the
presence of a base selected from the group consisting of potassium
hydroxide, calcium hydroxide and magnesium hydroxide.
Recent results indicate that potassium hydroxide affords superior
delignification to sodium hydroxide in both soda and soda/AQ
pulping of both un-extracted and hot water pre-extracted (HWP-E)
chips. A weaker base such as Ca(OH).sub.2 or Mg(OH).sub.2 may be
able to replace NaOH or KOH for HWP-E chips that are easier to
delignify. We have also performed pulping trials with Mg(OH).sub.2
and oxygen.
The pulping step, in another preferred embodiment, is carried out
by a combination of mechanical and chemical pulping. This process,
sometimes referred to as a semichemical process, is essentially a
chemical delignification process in which the chemical reaction is
stopped at the point where mechanical treatment is necessary to
separate fibers from the partially cooked lignocellulosic
materials. Any of the chemical pulping processes discussed above
may be utilized in the chemical pulping phase of the combined
mechanical and chemical pulping operation. In view of the
similarity of between chemical processing and a combination of
mechanical and chemical processing, this processing step is denoted
in FIG. 3 by the same reference numeral employed to designate
chemical pulp processing, reference numeral 8.
The pulp 9, produced in the mechanical pulping step 7 or the pulp
10 produced in the chemical pulping or the combination of
mechanical and chemical pulping step 8, is thereupon bleached in a
bleaching step 11.
In the preferred embodiment wherein pulp 9, produced by mechanical
pulping 7, is bleached, it is preferred that bleaching be
accomplished by contacting the pulp with a strong oxidizing agent.
A particularly preferred oxidizing agent employed in this bleaching
step is hydrogen peroxide.
In the preferred embodiment wherein pulp 10, prepared by chemical
pulping or by a combination of chemical and mechanical pulping, is
bleached, bleaching is effectuated by contacting the pulp with an
oxidizing agent selected from the group consisting of oxygen,
hydrogen peroxide, ozone, peracetic acid, chlorine, chlorine
dioxide, a hypochlorite anion and mixtures thereof.
In one particularly preferred embodiment, the pulp 10 is bleached
in two oxygen-contacting stages. In that preferred embodiment, it
is desirable that there be a washing step between the two
oxygen-contacting stages. Alternatively, that preferred embodiment
with oxygen and sodium hydroxide between the two oxygen-contacting
stages.
In another preferred embodiment, the bleaching of pulp 10 includes
contacting pulp 10 with chlorine dioxide in the presence of at
least one additional agent. In one preferred embodiment, the
additional agent is oxygen. In another preferred embodiment, the
additional agent is magnesium hydroxide or another
magnesium-contacting compound. In yet another preferred embodiment
the additional agents are oxygen and magnesium hydroxide or another
magnesium containing compound. In still another preferred
embodiment, the additional agent is potassium hydroxide or calcium
hydroxide.
In a second aspect of the present invention the initial step, prior
to hot water extraction, involves a biopulping step 4 wherein a
charge of a lignocellulosic material is contacted with at least one
fungus that breaks lignin-carbohydrate complexes (LCC) in
lignocellulosic materials. Preferably, fungi which degrade lignin
are utilized. Particularly preferred fungi of this type are species
of Cerioporiopsis, Trametes and Phlebia. These fungi exude a
lignin-degrading enzyme which permit their digestion of lignin.
Upon contact, the fungus grows on the lignocellulosic material at a
relatively slow rate compared to normal processing time scales in
the pulp industry. The treatment of lignocellulosic material with
at least one LCC breaking fungus, preferably a lignin-degrading
fungus, can take anywhere from two to six weeks or longer depending
on the degree of treatment desired. The treatment time can be
shortened by using greater concentrations of fungi initially but
this comes at higher cost. Previous related work has indicated that
the inoculation amounts (5 g/ton of lignocellulosic material) and
treatment time of 2 weeks are reasonably feasible from an economic
standpoint. Moreover, the use of a biological agent does not cause
contamination or health concerns relating to concentrated cultures
of microorganisms since the organisms used are all
naturally-occurring and limit their attack to lignocellulosic
materials.
As stated above, in this preferred embodiment the fungus-treated
lignocellulosic material is thereafter subjected to the
aforementioned hot water treatment. The product of the fungus
biotreatment 2, an enzyme extract 4 is separated and may or may not
be recovered. In the preferred embodiment wherein the enzyme is
recovered, the recovered enzyme is donoted by reference numeral 5.
That enzyme extract 5 is obtained as a course broth or as a
pressate, obtained by the application of mechanical pressure to the
fungus-treated lignocellulosic material. A concentrated broth is
thereupon formed by centrifugation. The recovered enzyme broth may
be utilized in subsequent steps of the process.
The biopulped lignocellulosic material is thereupon treated in
accordance with the first discussed embodiment of the process of
the present invention. That is, the biopulped lignocellulosic
material is subjected to the hot water extraction step 3 whereafter
the lignocellulosic material is pulped. Again, pulping is
effectuated by mechanical pulping, chemical pulping or a
combination of mechanical and chemical pulping.
It is emphasized that the aqueous extract, obtained in the water
extraction step 3, is processed in accordance with the method
discussed supra to obtain acetic acid and hemicellulose aqueous
solutions.
In the preferred embodiment wherein mechanical pulping is utilized,
the pulping processing is, but for one aspect, substantially
identical to mechanical pulping in the first preferred embodiment.
That aspect is the optional introduction of a LCC breaking enzyme,
preferably a lignin-degrading enzyme, into the mechanical pulping
operation 7. In one preferred embodiment that enzyme is provided by
the enzyme-containing crude broth 5 recovered in the biopulping
step 2. Alternatively, in an embodiment wherein the enzyme product
4 of the fungal biotreatment step 2 is not recovered, fresh enzyme
6 may be co-introduced, with the pulp, into the mechanical pulping
step 7. The introduction of enzyme into the mechanical pulping step
7 increases the rate of pulping insofar as the enzymatic removal of
lignin reduces the mechanical work necessary to accomplish the same
task.
In an alternate embodiment of the second aspect of the instant
process, pulping is performed by chemical pulping or a combination
of mechanical and chemical pulping, denoted by reference numeral 8.
In this processing step, the lignocellulosic materials subjected
upstream to hot water processing step 3 are pulped in accordance
with the process of chemical pulping discussed in the first aspect
of the process described supra.
The pulp 9, produced in the mechanical pulping step 7, or the pulp
10, produced in the chemical pulping or the combination of
mechanical and chemical pulping step 8, is next bleached in
bleaching step 11. In this step the pulp is whitened without
adversely affecting the strength of the fibers. Bleaching step 11
in this second aspect of the present invention is conducted in
accordance with the bleaching step within the contemplation of the
first aspect of the process of the present invention. There is,
however, one additional preferred processing step in the second
aspect of the process of the present invention. That is,
independent of whether pulp 9, generated by mechanical pulping, or
pulp 10, generated by chemical pulping or a combination of
mechanical pulping and chemical pulping, is bleached, the
additional processing step of introducing an enzyme that breaks LCC
bonds into the bleaching reactor is included. Preferably, that
enzyme is a lignin-degrading enzyme. That enzyme may be obtained
from vendors marketing such enzymes or may be the enzyme recovered
from the biopulping step, e.g. the biopulping step, e.g. the
fungus-lignocellulosic contacting step. These alternatives are
illustrated in the drawings by enzyme 6 and recovered enzyme 5,
respectively introduced into bleaching step 11.
The process of the second aspect of the process of the present
invention, like the process of the first aspect of the process of
the present invention, includes the step of combusting and
recovering the energy values of the charge of the lignocellulosic
materials not subjected to pulping and bleaching.
A third aspect of the process of the present invention involves the
steps of pulping and bleaching a charge of lignocellulosic
material. In that process a charge of lignocellulosic material is
pulped to provide individual fibers and fiber bundles. The pulping
step in this aspect of the present invention may be accomplished by
mechanical pulping, chemical pulping or a combination of mechanical
and chemical pulping. The preferred embodiments of these pulping
methods, discussed supra, in regard to the first two aspects of the
present invention, may be utilized.
The pulped product, in this third aspect of the present invention
is bleached. This bleaching step involves contacting the pulped
product with chlorine dioxide in the presence of an agent selected
from the group consisting of oxygen, magnesium hydroxide, another
magnesium-containing compound, oxygen and magnesium hydroxide or
another magnesium-containing compound, potassium hydroxide and
calcium hydroxide.
The specific bleaching procedures discussed supra, may all be
utilized in effectuating bleaching of the pulped product. Thus,
detailed preferred embodiments of bleaching, as discussed in the
first aspect of the present invention are incorporated by
references in detailing preferred embodiments of the instant third
aspect of the present invention.
A fourth aspect of the present invention focuses upon another
process of pulping and bleaching lignocellulosic materials. In this
fourth aspect a charge of lignocellulosic material is contacted
with a fungus that breaks LCC in the lignocellulosic material. This
contact yields a biopulped lignocellulosic material and an enzyme
product produced by the fungus. The enzyme product is separated and
the fungus-contacted lignocellulosic material is pulped. The pulp
product of the pulping step is thereupon bleached. The
fungus-contacted lignocellulosic material not subjected to pulping
and the pulp product of the pulping step not subjected to bleaching
is combusted to recover the energy value of the charge of
lignocellulosic material not utilized in recovering product
values.
A further requirement of this aspect of the process of the present
invention is that the bleaching step include introduction of an
enzyme that breaks LCC into the bleaching apparatus, along with the
pulp. In a preferred embodiment that enzyme is provided by the
enzyme separated from initial charge of lignocellulosic material
contacted by the fungus that breaks LCC.
Preferred embodiments concerning the details of the pulping and the
bleaching steps are discussed above, in the discussion of the
second aspect of the present invention and hereby incorporated into
the detailed description of this fourth aspect of the present
invention.
A fifth aspect of the present invention is the novel pulp produced
by the first and second aspects of the present invention which
includes a hot water extraction of the charged lignocellulosic
materials. That pulp is characterized by a specific surface are in
the range of between about 5,000 cm.sup.2/g and about 40,000
cm.sup.2/g and a specific volume in the range of between about 1.5
cm.sup.3/g and about 4.0 cm.sup.3/g. Preferably, the pulp of the
present invention has a specific surface area in the range of
between about 15,000 cm.sup.2/g and about 25,000 cm.sup.2/g and a
specific volume in the range of between about 2.75 cm.sup.3/g and
about 3.75 cm.sup.3/g.
The following examples are given to illustrate the scope of the
present application. Because these examples are given for
illustrative purposes only, the present invention should not be
deemed limited thereto.
EXAMPLE 1
Picea abies Preparation
Picea abies (Norway spruce), a softwood was utilized in this
example. However, different species of woods, including hardwoods
and/or softwoods, can also be used. Moreover, the invention can be
used with virgin wood or waste wood, including, e.g., kiln dried,
air-dried and green wood from industrial, residential, sawmill,
construction and demolition sources. In the present example, logs
from a 79-year old tree were debarked with a 36-cm spoke shave,
chipped in a Carthage 10-blade chipper, and air dried to
approximately 15% moisture by spreading the chips on a tarp. The
chips were then screened in a Williams classifier. All fractions
were collected and the chips retained on 15.8, 12.7 and 9.25-mm
screens were pooled together and sealed in plastic bags, and stored
at room temperature (approximately 24.degree. C.) for use
throughout this study. TAPPI test method T-257 cm-97 was followed
for all subsequent testing and samples were taken from the pooled
material as needed.
TAPPI refers to the Technical Association of the Pulp and Paper
Industry, Norcross, Ga. The subject areas for TAPPI Test Methods
and their numbering are: (a) Fibrous Materials and Pulp Testing, T
1-200 Series, (b) Paper and Paperboard Testing, T 400-500 Series,
(c) Nonfibrous Materials Testing, T 600-700 Series, (d) Container
Testing, T 800 Series, (e) Structural Materials Testing, T 1000
Series, and (f) Testing Practices, T 1200 Series. The suffix
following the Test Method number indicates the category of the
method. Test Method numbers consist of a capital T, followed by a
space, then a number (assigned sequentially within several Test
Method categories), another space, a two-letter designation of
classification, a hyphen, and the last two digits of the year
published. The two-letter designations for classifications are: (a)
om=Official Method, (b) pm=Provisional Method, (c) sp=Standard
Practice, and (d) cm=Classical Method.
Fungal Pretreatment of Wood Chips
TAPPI test method T-412 om-94 was followed for moisture content
determination. A 1500 g OD sample was weighed out for each
bioreactor and brought up to 50% moisture content by soaking in
distilled water. Bioreactors were cleaned and sterilized with a 10%
(v/v) commercial Clorox bleach/90% water solution and rinsed with
distilled water. Chips were layered in the reactor with 600 g on
each layer; the reactor was loosely sealed with an aluminum foil
cap covering the vent in the lid and then steamed for 10-minute
under atmospheric conditions. The reactor was then cooled for
approximately two hours until the temperature was below 30.degree.
C. The moisture content was brought up to 55% moisture by the
addition 200 ml water collected during steaming plus additional
distilled makeup water. Fresh fungal inoculum (2.3 ml) and 0.5%
(v/v) unsterilized corn steep liquor (CSL) at 50% solids was added
to the additional distilled makeup water. The fungal inoculum/corn
steep liquor mixture, diluted with the distilled makeup water, was
poured over the chips in the bioreactor and the cover replaced.
Generally, the chips can be inoculated with the lignin-degrading
fungus by providing a liquid mixture including the fungal inoculum,
and applying the liquid mixture to the chips. The inoculated chips
were then incubated under conditions favorable to the propagation
of the lignin-degrading fungus through the chips. Specifically, the
bioreactor was then placed in the incubation chamber at 27.degree.
C. with forced continuous flow of warm humidified air at a rate of
0.028 cubic meters per minute. House air was measured by a flow
meter and humidification was controlled by passing air through two
water filled two-liter glass sidearm flasks (in series) through a
fritted ground glass sparger. The sidearm flasks were immersed in a
40.degree. C. water bath. From the hot water flasks, the warm
humidified air passed though a water trap and a final filtering
through a 0.2 micron Millipore air filter (for sterilization)
before connecting to the individual bioreactors.
At daily intervals, the warm humidified air flow-rate was measured
and corrected if needed and the chips were checked for
contamination. At weekly intervals, the water trap in the bottom of
the incubation locker was emptied and one layer of chips was
removed from the reactor placed in a plastic bag, sealed and frozen
at -20.degree. C. until further processing.
TMP Refiner Mechanical Pulp Production (KRK)
Air-dried and screened Picea abies wood chips (800 g OD) were
brought up to 10% moisture content and placed in the sample hopper
on the pressurized refiner (Kumagai Riki Kogyo Co. Ltd., Tokyo,
Japan, Model BRP45-30055). Low-pressure steam (32 kpa.sub.g)
softened the wood chips for three minutes. The TMP produced was
sealed in a 40-liter Nalgene.RTM. carboy and refrigerated at
4.degree. C. until use.
Culture Supernatant Purification
Purification involved monitoring laccase and manganese peroxidase
activity and harvesting the mycelium from P. subserialis
(RLG6074-sp), C. subvermispora (L-14807 SS-3), and T. versicolor
(FP-72074) on the first day after peak laccase activity. Mycelium
was harvested from the liquid culture by centrifuging for 20 min at
10,000 rpm, followed by treating the crude supernatant with 10%
(v/v) acetone and refrigerating for one hour at 4.degree. C. to
precipitate any extracellular polysaccharide. The broth was
centrifuged again for 20 minutes at 10,000 rpm and filtered through
a Whatman glass microfiber GF/A 42.5-mm diameter filter. The
resulting supernatant was concentrated in a DC-2 ultrafiltration
unit (Amicon Corp., Danvers, Mass.) equipped with a 30-kDa
molecular weight cutoff hollow fiber filter from an initial volume
of 1000 ml to 100 ml. Enzyme activity was monitored at harvest time
and after the final concentration.
Enzyme Treated TMP
First-stage coarse thermomechanical pulp was treated with partially
purified culture supernatant from P. subserialis, C. subvermispora,
and T. versicolor at a dosage determined by normalizing to a
manganese peroxidase enzyme activity of 1500 nkatal 1.sup.-1.
Duplicate reaction vessels contained 2.0 g OD coarse refiner
mechanical pulp that was suspended in 5% (w/v) 50-mM sodium acetate
buffer (pH 4.5). The pulp in each reaction vessel was mixed with
concentrated enzyme broth at a normalized enzyme activity of
approximately 1.50 nkatal ml.sup.-1 manganese peroxidase. Laccase
activity was measured and monitored throughout the experiment. For
each fungus, one reaction vessel was setup in duplicate for
analysis at 0, 30, 60, 90, 180 and 360-minute intervals in a
constant temperature bath of 30.degree. C. Initial and final
laccase and manganese peroxidase enzyme activity were measured for
each time interval followed by a complete lignin analysis at each
time interval to evaluate the effect of the enzymes on refiner
mechanical pulp.
Soxhlet Resin Extraction
TAPPI test method T-264 cm 97 details the procedure followed to
report chemical analysis on an extractive free basis. Air-dried
Wiley milled samples (approximately 10.0 g) of both pretreated wood
samples and mechanical pulp were placed in an OD tarred
45.times.105-mm extraction thimble. The extraction thimble was
placed into a 50-mm Soxhlet extractor fitted with an Allihn
condenser and a 500-ml round bottom three-neck flask (FIG. 11).
Boiling chips were added to the boiling flask with 300 ml of the
ethanol-benzene mixture. Samples were extracted for eight hours at
brisk boiling with siphoning at approximately ten-minute intervals.
After eight hours, the extraction thimbles were removed from the
Soxhlet extractors, washed with 100% pure ethanol by placing the
thimble in a 100 ml coarse ground glass crucible fitted on a
1000-ml sidearm flask. The thimble was returned to the Soxhlet
extractor and extracted for four hours with 100% pure ethanol. The
samples were transferred to a Buchner funnel and washed with hot
water to remove the ethanol and then allowed to air dry for all
subsequent carbohydrate and lignin analyses.
Enzyme Extraction from Wood Chips
Picea abies chips were prepared as previously described, inoculated
with Phlebia subserialis, Ceriporiopsis subvermispora, and Trametes
versicolor, and incubated for 30 days at 27.degree. C. with forced
warm humidified air at a rate of 0.028 cubic meters per minute. The
chips were thus incubated under conditions favorable to the
propagation of the lignin-degrading fungus through the chips.
Duplicate 500-g samples were removed from each bioreactor, and
double-bagged in 6.times.9 zip lock bags. One bottom corner of the
double bag was cut off with scissors. The stainless steel plates on
the top and bottom pressing surfaces of the Williams press
(Williams Apparatus Co., Watertown, N.Y.) were cleaned first with
soap and water and then dried with ethanol. The press was blocked
up at a 45.degree. angle and secured. The zip lock bag containing
the sample was placed between the pressing surfaces and a clean
20-dram vial was placed under the cut corner of the bag. Pressure
was applied (1500 psi) to the sample and the pressate was captured
in the glass vial as a crude broth. Laccase and manganese
peroxidase enzyme assays were performed on each vial to determine
the enzyme present and enzyme concentration.
Enzymatic Treatment of TMP
Extracellular lignolytic enzymes secreted into the production and
growth media were identified, monitored for peak concentration
within the production media, harvested for additional
experimentation and finally concentrated ten-fold. The broth was
centrifuged for 20 minutes at 10,000 rpm and filtered through a
Whatman glass microfiber GF/A 42.5-mm diameter filter. The
resulting supernatant was concentrated in a DC-2 ultrafiltration
unit (Amicon Corp., Danvers, Mass.) equipped with a 30-kDa
molecular weight cutoff hollow fiber filter from an initial volume
of 1000 ml to 100 ml. Laboratory analysis of fungal growth
established the initial growth conditions and approximate
harvesting time for peak production. The enzyme concentration was
then adjusted to 1.4 nkatal/ml and were used to treat
1.sup.st-stage TMP as a method to reduce the amount of lignin
within the pulp, reducing the electrical refining energy and
thereby increasing pulp strength. This system can also be used as a
first-stage biobleaching of mechanical pulp. Throughout the
experiment, the enzyme activity levels were monitored, followed by
a lignin analysis of the TMP. Table 1 lists the laccase and
manganese peroxidase enzyme activity levels throughout the pulp
treatment. Initial activity was measured from the concentrated
production medium before addition to each sample and then the
manganese peroxidase enzyme concentration was normalized to
approximately 1.50 nkatal ml.sup.-1 for the zero-time condition.
The laccase and manganese peroxidase activities were measured and
monitored for the change in activity over time.
TABLE-US-00001 TABLE 1 Enzyme activity change over the 6-hour
treatment time of thermomechanical pulp with partially purified
lignolytic enzymes from P. subserialis, T. versicolor and C.
subvermispora Initial 0 30 60 90 180 360 Activity minute minute
minute minute minute minute P. subserialis harvested at 7 days
Laccase (nkatal/ml) 12.15 7.63 7.45 7.55 6.67 6.26 5.95 MnP
(nkatal/ml) 2.42 1.52 1.49 1.42 1.37 1.32 1.28 T. versicolor
harvested at 10 days Laccase (nkatal/ml) 1849.8 822.6 819.2 815.4
813.5 811.0 797.2 MnP (nkatal/ml) 3.62 1.61 1.59 1.57 1.53 1.52
1.46 C. subvermispora harvested at 12 days Laccase (nkatal/ml)
864.9 864.9 865.2 862.4 858.8 854.2 852.7 MnP (nkatal/ml) 1.56 1.56
1.54 1.49 1.38 1.27 1.16
Laccase from P. subserialis showed a 22% decrease in activity while
T. versicolor and C. subvermispora showed much smaller changes in
activity, 3.1 and 1.4%, respectively. This difference may not be
significant due to the much lower laccase activity in the enzyme
broth from P. subserialis. Initial manganese peroxidase activity
levels were on the same order of magnitude for all three fungal
extract applications. The range in overall manganese peroxidase
activity loss was from 15.8% for P. subserialis to 8.9 and 25.7%
loss for T. versicolor and C. subvermispora, respectively.
FIGS. 1 and 2 chart the enzyme activity throughout the experiment
and show the decrease in activity over the life of the experiment.
In particular, FIG. 1 illustrates the lignolytic enzyme activity
change for the laccase enzyme, where thermomechanical pulping (TMP)
is performed over a six hour treatment time on Picea abies (Norway
Spruce) wood chips with fungal treatment using P. subserialis, T.
versicolor and C. subvermispora. FIG. 2 illustrates the lignolytic
enzyme activity change for the manganese peroxidase enzyme, for
comparison with the results of FIG. 1. In FIG. 1, the horizontal
axis denotes time, in minutes, from 0 to 400 minutes, while the
left hand vertical axis denotes T.v. and C.s. laccase activity, and
the right hand vertical axis denotes P.s. laccase activity. In FIG.
2, the horizontal axis denotes time, in minutes, from 0 to 400
minutes, while the left hand vertical axis denotes manganese
peroxidase activity.
Table 2 outlines the results from lignin analysis on the TMP,
showing that the lignolytic enzyme treatment from C. subvermispora
removed up to 3.66% of the lignin in the sample over a six-hour
period, while P. subserialis and T. versicolor reduced the lignin
content by similar amounts, 2.35 and 2.67%, respectively. P.
subserialis showed a significant decrease in lignin content at the
90-minute sample; however, no significant change occurred after
that time interval. Both T. versicolor and C. subvermispora
appeared to continually decrease lignin content throughout the
experiment. A longer running experiment is expected to show greater
lignin losses with increased treatment time, with the enzyme
activity monitored as a theoretical stopping point. These small
changes in the lignin content are significant because they compare
with a one to two week biopretreatment stage.
TABLE-US-00002 TABLE 2 Klason lignon analysis of a Picea abies TMP
treated with partially purified enzymes from P. subserialis, T.
versicolor and C. subvermispora over 6 hours Time Total Standard
Percent Loss Fungus (min) Lignin (%) deviation (%) Control 0 29.21
0.29 0 Phlebia subserialis 30 29.17 0.12 0.14 60 28.71 0.18 1.74 90
28.52 0.60 2.42 180 28.64 0.04 1.99 360 28.54 0.23 2.35 Trametes
versicolor 30 28.86 0.20 1.21 60 28.61 0.53 2.10 90 28.92 0.07 1.00
180 28.35 0.25 3.03 360 28.45 0.33 2.67 Ceriporiopsis 30 29.28 0.05
-0.24 subvermispora 60 28.70 0.33 1.78 90 28.77 0.10 1.53 180 28.20
0.38 3.58 360 28.18 0.40 3.66
Lignolytic Enzyme Activity Extracted from Picea abies
Fresh Picea abies samples were treated with the three species of
white-rot fungi to identify the enzymes present in the internal
wood structure, measure the activity level and make comparisons
with enzyme production under laboratory conditions (Table 3). A
novel procedure for isolating extracellular enzymes present within
the internal wood structure allowed the comparison. Specifically,
duplicate 500-g samples were removed from each bioreactor, and
double-bagged in 6.times.9 zip lock bags. One bottom corner of the
double bag was cut off with scissors. The stainless steel plates on
the top and bottom pressing surfaces of the Williams press were
cleaned first with soap and water and then dried with ethanol. The
press was blocked up at a 45.degree. angle and secured. The zip
lock bag containing the sample was placed between the pressing
surfaces and a clean 20-dram vial was placed under the cut corner
of the bag. Pressure was applied (1500 psi) to the sample and the
pressate was captured in the glass vial. The ability of P.
subserialis to repeatedly produce laccase under biopulping
conditions was significant due the inability to repeatedly produce
detectable activity in the laboratory under controlled conditions
with this organism. There were large variations in detectable
enzymes and activity levels under laboratory conditions and the
ability to characterize the fungi under non-induced conditions,
while growing in a biopretreatment environment, hold significant
potential.
TABLE-US-00003 TABLE 3 Comparison of laccase and manganese
peroxidase enzyme activity from P. subserialis, T. versicolor and
C. subvermispora; Extracted from Picea abies and laboratory growth
conditions Picea abies Laboratory enzyme activity .+-. std. enzyme
activity dev. at harvest time Phlebia subserialis Laccase 3.66 .+-.
0.07 4.47 @ 7 days (nkatal/ml) Manganese 0.742 .+-. 0.03 0.229 @ 7
days peroxidase (nkatal/ml) Trametes versicolor Laccase 3.01 .+-.
0.00 676.5 @ 10 days (nkatal/ml) Manganese 1.25 .+-. 0.05 0.594 @
10 days peroxidase (nkatal/ml) Ceriporiopsis subvermispora Laccase
2.92 .+-. 0.2 214.2 @ 12 days (nkatal/ml) Manganese 0.322 .+-.
0.014 1.61 @ 12 days peroxidase (nkatal/ml)
EXAMPLE 2
All hot water pre-extraction (HWP-E) for this example were done in
M&K digesters. Alkaline pulping was conducted in the M&K
digesters as well or in small autoclaves placed into the M&K
digesters. Pin chips were used in the autoclaves. The extent of
HWP-E varied from mild to severe.
The pulping parameters were adjusted for the cooking of pin chips
since these cooks were done in 250 mL autoclaves. The cooking
parameters were: AA 24%, Sulfidity 26%, and L:W 10:1. The
autoclaves were brought up to 170.degree. C. in 90 minutes and held
there for 60, 120, and 180 minutes.
The extracted sugar maple pin chips were done similarly. The
cooking parameters, except for the temperature profiles, were the
same. These cooks were brought up to 170.degree. C. in 60 minutes
and held there for 15, 30, and 60 minutes consecutively.
Kappas and Viscosity Done to TAPPI Standard Methods
Exploratory Cooks for Yield Optimization
The exploratory cooks were carried out on standard sugar maple
chips for yield optimization. The HWP-E was not separated from the
cooks; that is the chips were left in the M&K digesters after
the HWP-E was drained and immediately delignified by way of three
types, Kraft, Kraft with polysulfide, and Soda AQ.
The standard controls on the three schemes were done on
non-extracted sugar maple chips. The control parameters are seen in
Table 1. In Table 1, the acrynym AA means active alkali
(NaOH+Na.sub.2S on a Na.sub.2O basis). The acrynym EA means
effective alkali (NaOH+1/2Na.sub.2S).
TABLE-US-00004 TABLE 1 Kraft Control Kraft with Poly sulfide
Control AA: 16% AA: 16% EA: 14% EA: 14% Sulfidity: 25% Sulfidity:
25% L:W 5:1 Polysulfie: 2% Sulfur 90 min .fwdarw. 165.degree. C.
L:W 5:1 120 min @ 165.degree. C. 90 min .fwdarw. 165.degree. C. 120
min @ 165.degree. C. Soda AQ Control AA: 14% AQ: 0.1%
Na.sub.2SO.sub.3: 0.5% L:W 4:1 90 min .fwdarw. 165.degree. C. 150
min @ 165.degree. C.
Lignin Leachability from Extracted Sugar Maple Chips
The extracted sugar maple chips delignify faster. This lead to the
desire to quantify the leachability of the lignin within both
extracted and non-extracted wood chips. Chips were HWP-E at 140,
150, and 160.degree. C. for this study.
The wood chips were separated into different 1/2 gal "Wiffle"
Reactors according to the temperatures at which they were
extracted. A portion of un-extracted wood chips was also put into a
"Wiffle" Reactor. These reactors are made in house and are named
such, because of their resemblance to a wiffle ball. That is the
reactor is cylindrically shaped with a plurality of openings even
spaced on its peripheral.
Each reactor was then submerged into a separate 4 L plastic beaker
containing a weak alkali solution. The solution was made up of 0.1
N sodium hydroxide at a 20:1 L:W ratio. This was an approximate
volume of 3.5 L. 10 mL samples were removed periodically over the
course of six days. The samples were then analyzed in a UV
spectrophotometer at the peak of 205 nm.
Void Volume
It is most likely that the free volumes within these wood chips are
being affected by HWP-E, that is under conditions where the chips
are swollen. This was determined by measuring the amount of water
encumbered by the chips. This was done on both non-extracted and
extracted wood chips. The extracted wood chips used in this method
were from both mild and severe HWP-E schemes.
A sample was placed into a desiccator filled with water and
attached to a vacuum pump. This is a sealed system. When the pump
was turned on, the chips slowly sink as the air is replaced with
water within their structures. After 2 hours, the pump was turned
off and floating chips were discarded.
The chips were then dried. The surfaces of the chips were dried of
any free water. Next their wet weight was recorded, and then placed
in a drying oven at 105.degree. C. over night. The next day the dry
weight of the chips were recorded. The difference between the two
weights is the mass of water absorbed into the wood chips. Assuming
standard conditions a volume was calculated for the water. Void
volume as seen in the results and discussion is volume over OD chip
mass, mL/g.
Kappa vs. Yield Relationship
After more severe HWP-E, the chips cook faster under alkaline
conditions. A kappa number of 17-18 can be obtained in 75 minutes,
of which 60 of those minutes are the ramp time to temperature. A
control cook on non-extracted wood chips took 210 minutes and was
at a digester yield 2 percentage points below that of the
extracted-Kraft cook as can be seen in FIG. 4. This can be
deceiving, because approximately 20% of the wood mass is removed
during severe HWP-E. So overall yield, pulp from chips prior to
pre-treatment, is lower than wood not extracted at all.
Viscosities were measured on Kraft pulp created from both extracted
and non-extracted wood chips. The pulp was from the autoclave
cooks. It is apparent that the extracted wood pulp has a higher
Degree of Polymerization (DP). This suggests that the cellulose is
damaged less, most likely because of the shorter cook times
involved. The lowest point on the pre-treatment line, i.e. HWP-E,
has just about the same viscosity as the highest value for the
control pulps (FIG. 5). Both of these points were pulped at 60
minutes at temperature. This further supports the fact that length
of time in the digesters seems to be the only variable affecting
cellulose degradation between the control and pre-treated chips
cooked under Kraft conditions. A viscosity of 31 cP at a Kappa
number of 7 is impressive.
Exploratory Cooks for Yield Optimization
Three types of alkaline cooking were done under less aggressive
HWP-E conditions to try to increase overall yield. The pHs of the
extracted liquor from the more severe extractions and milder ones
were similar. This supports the fact that the same amount of
deacetylation was occurring in the milder extractions as in the
more intense. However, the hemicellulose removal in the harsher
HWP-E was much higher.
Three different alkaline pulping techniques were investigated
(Table 2) and the non-sulfur Soda AQ process gave higher yields
than the Kraft after identical HWP-E treatment (Table 3). The same
EA (14%) was used for both processes and the soda/AQ process gave a
higher pulp yield even though its retention time in the alkali was
longer (Table 2). This was also observed at another HWP-E treatment
condition. The HWP-E might have produced more reducing end groups
in the carbohydrate fraction. Oxidation of these end groups to
carboxylic acids by AQ would decrease the rate of alkaline peeling
during pulping.
TABLE-US-00005 TABLE 2 Cooking Times (mins) Extraction Temperature
(.degree. C.) Controls 140 150 160 Kraft 90 min --> 165.degree.
C. 60 min --> 165.degree. C. 120 min @ 165.degree. C. N/A N/A 60
min @ 165.degree. C. Kraft with 60 min --> 165.degree. C.
polysulfide* N/A N/A N/A 60 min @ 165.degree. C. Soda AQ 90 min
.fwdarw. 165.degree. C. 60 min .fwdarw. 165.degree. C. 60 min
.fwdarw. 165.degree. C. 60 min .fwdarw. 165.degree. C. 150 min @
165.degree. C. 120 min @ 165.degree. C. 120 min @ 165.degree. C.
120 min @ 165.degree. C. *2% sulfur from polysulfide
TABLE-US-00006 TABLE 3 Yields (%) Extraction Temperature (.degree.
C.) Controls 140 150 160 Kraft 51 N/A N/A 47.7 Kraft with N/A N/A
N/A 49.0 polysulfide Soda AQ 51.2 52.3 51 48.9
Lignin Leachability from Extracted Sugar Maple Chips
Delignification is amplified as seen by the decrease in Kraft
cooking times. Lignin's leachability is improved significantly by
HWP-E. As temperature is increased during the HWP-E, the rate at
which lignin can be removed under mild alkali conditions (0.1M NaOH
and .about.25.degree. C.) is increased as well. This can be seen in
FIG. 6.
The data shown in FIG. 6 measures the concentration of soluble
lignin leached out of both control and extracted chips into
solution. The bottom set of points represent non-extracted sugar
maple, and consecutively above them chips extracted at increasing
temperatures.
Void Volume
Both the diffusion of pulping chemicals into a chip and diffusion
of lignin out should increase with an increase in void volume. The
importance of void volume on the enhancement on the rate of
alkaline pulping is presently being investigated. As would be
expected, the higher temperature and/or times these chips are
extracted at, more mass is removed. This is consistent with the
increase of void volume within the chips (FIG. 7).
Bleachability of Pulps
In one example a mixture of hardwood chips was given a HWP-E
treatment and .about.20% of the mass was removed. The HWP-E and
un-extracted chips were both cooked to .about.17 kappa number by
the kraft process. When bleached by the DE.sub.pD sequence, the
pulp from the un-extracted chips achieved a brightness of 86.3%
while the HWP-E pulp achieved a brightness of 91.6%. In a second
example, HWP-E was used to remove 12% of the mass from sugar maple
chips. After soda/AQ pulping a kappa number of 16.5 was obtained.
After our standard oxygen delignification the kappa number
decreased by 61% to 6.5. The O.sub.2 delignification results for a
wide range of hardwood chemical pulps under the same standard
conditions are given in Table 4. The largest decrease in kappa
number was 53%.
TABLE-US-00007 TABLE 2 Decrease in kappa number of Conventional
Hardwood Kraft Pulps caused by O.sub.2 delignification. Pulping
Process Chip Furnish Unbl. Kappa O.sub.2 Kappa % Decrease KL.sup.1
Sugar Maple 18.5 9.9 46 KL MBA.sup.2 18.0 8.5 53 KL MBC.sup.3 17.4
10.1 42 KL HP 1.sup.4 20.6 10.6 49 KL HP 2 17.0 8.2 52 KL HP 3 13.3
7.2 46 KU -- 13.7 8.6 37 KQU -- 17.2 10.4 40 SAQ1 Sugar Maple 15.4
9.0 42 SAQ2 HP 2 16.2 8.7 46 SAQ3 HP 3 14.0 7.3 48 .sup.1KL = Kraft
in lab; KU = Kraft in mill (conditions unknown); KQU = Kraft/AQ in
mill; SAQ = soda/AQ .sup.2Maple/birch/cottonwood (1:1:1)
.sup.3Maple/birch/aspen (1:1:1) .sup.4HP = hybrid poplar
In a third example a mild HWP-E was used to extract .about.5% of
the wood mass. Mild HWP-E is normally conducted for shorter times
but with the addition of a small dose of acetic acid. In commercial
practice, this acetic acid would be obtained by recycling some of
the HWP-E effluent. Soda/AQ pulping was performed in accordance to
Table 2 but for 90 instead of 120 minute. A 31 kappa number pulp
was obtained but oxygen delignification decreased its kappa number
by 72% to 8.8.
Conclusions
The chemical and physical properties of the wood are changed from
this extraction process. Changing the material, changes the
parameters required for alkali pulping. It has been observed that
these extracted wood chips delignify faster to equivalent kappa
numbers and yields of non-extracted wood chips. It has also been
observed that higher yields can be obtained at the expense of
higher kappa numbers, but these HWP-E pulps are easier to bleach,
even Soda AQ pulps.
The harsher HWP-E does reduce the overall yield of a pulping
process. Components removed are predominantly hemicelluloses, which
do not add significantly to the final product as far as structural
strength. It can be debated that it does act as an adhesive between
fibers.
The milder extractions used to achieve competitive yields to
conventional pulping only remove hemicelluloses to the extent of
.about.5% based on chip weight. This may be ideal for pulp mills,
considering the shorter cooking times, higher yields, and better
bleach-ability and the removal of sulfur from the process. Besides
the fact, acetic acid is a higher value commodity as compared to
ethanol from fermentation of extracted sugars, which likely
requires greater capital than acetic acid separation. If a pulp
mill were not to take advantage of the acetic acid market, very
little capital would be required to modify an existing process.
A shorter time in the digester has a positive affect on the degree
of polymerization of cellulose and most likely sheet strength. This
has not been substantiated yet by making handsheets, but is a
strong assumption. Soda AQ may be a good way to cook these
extracted sugar maple chips. Eliminating sulfur would greatly
simplify the recovery system and likely improve energy
efficiency.
EXAMPLE 3
Materials and Methods
Preparation of the Chips
Wood chips arrived in barrels from the SUNY-ESF Genetics Field
Station in Tully, N.Y. The chips were from a single harvest at four
years of age of a multi-clone trial. The chips were laid out for
two weeks to air dry with a resulting oven-dry (OD) solids content
of 92.3%. After air-drying, the chips were well-mixed and then
divided and placed into large plastic bags for storage. It was
important to bring the chips to a constant and low moisture content
to ensure natural degradation did not take place during storage.
When chips were needed for treatment, a 1625 gram air-dry (AD) chip
sample (1500 g OD) was brought up to a 50% moisture content by
soaking overnight in distilled water. Xylan in wood is fairly
resistant to leaching at low temperatures due to the molecular size
of the polymer molecule. The soaking was done at room temperature
to minimize the loss of xylan during this step.
The chips were then incubated in an aerated static bed-bioreactor
consisting of 21-L polypropylene containers. The lid on the
containers vented to the atmosphere through an exit tube. At the
bottom of the polypropylene container, a 1-cm side opening provided
for controlled inlet airflow.
Prior to inoculation, the clean, empty bioreactors were autoclaved
for twenty minutes. After the chips were added to the vessel, steam
was injected for thirty minutes through latex tubing connection at
the bottom of the reactor. The bioreactors' lids were left slightly
ajar to prevent over pressurization. After steaming, the bioreactor
was drained to remove the excess water that had condensed inside
the vessel. The vessel and its contents were then cooled for two
hours before inoculation, with the inlet and outlet of the vessel
covered with aluminum foil to avoid contamination.
Preparation of the Inoculum
C. subvermispora strain L14807 SS-3 (Cs SS-3) was obtained from the
USDA Forest Service, Forest Products Laboratory (FPL) in Madison
Wis. All stock culture slants were incubated at 26.degree. C.,
stored at 4.degree. C., and maintained at 2% (w/v) potato dextrose
sugar plates. The samples were prepared and maintained as reported
in Example 1.
When needed for treatment, 2.31 ml of mycelium was added to 100 ml
of sterile water and blended for 75 seconds. The blending was done
in 15-second intervals followed by a 15-second pause to avoid heat
build up, up to a total of 75 seconds of blending. The blended
mycelium was transferred to a sterile beaker, additional makeup
water was added to bring the chips to a 55% moisture content, and
0.5% unsterilized corn steep liquor at 50% solids added to the
beaker. The mixture was then poured over the chips in the
bioreactor and mixed by shaking the bioreactor.
The bioreactors were then incubated at 27.degree. C. with an
airflow of 7.87 cm.sup.3/s (1.0 ft.sup.3/h) per bioreactor. The air
was humidified by flowing through two water-filled 2-L Erlenmeyer
flasks through a fritted ground glass sparger. The humidified air
passed through a water trap, filtered through a 0.2 .mu.m Millipore
filter, and entered the base of the bioreactor.
After the two weeks, the chips were removed from the incubator and
frozen to prevent any further fungal growth prior to the analysis
or subsequent extraction. The chips were kept frozen until 12 hours
before they were used for xylan extraction.
Hot Water Extraction
Hot water extraction was carried out in a 4-L capacity M&K
digester equipped with indirect heating through heat exchangers
with forced liquor recirculation. The basket was filled with chips
(1500 g OD) from air-dried willow samples for the control. For
pretreated samples, the chips were removed from the freezer allowed
to thaw for 12 hours. The basket was placed in the digester and
distilled water was added to achieve a 4:1 liquor to wood ratio.
The digester cover was then closed and the circulation pump turned
on. The temperature was set (experiments were at 140.degree. C.,
145.degree. C., 150.degree. C., 155.degree. C. and 160.degree. C.)
and the heaters were turned on. The chips were brought up to
temperature in approximately 15 minutes and the two-hour extraction
began.
After the two-hour extraction, the pump and heater were turned off
and a bottom valve opened slowly to relieve the pressure and to
withdraw the extract for analysis. The extract was collected
through a valve and heat exchanger to cool the sample below the
boiling point. The chips were washed thoroughly until a clear
liquid was observed. The wash water was not collected. The chips
were then placed in a drying oven at 105.degree. C. overnight to
determine the mass loss of the chips.
Extractant Composition
After the pH of the extract had been determined, a sample of the
extractant was then evaporated in a 105.degree. C. oven to
determine both the solids content and to prepare a sample for the
carbohydrate analysis. A 100 to 200-ml portion of the extractant
was placed in small porcelain crucibles and evaporated at
105.degree. C. in a drying oven for 3 days or until a stable weight
had been achieved. The sample was weighed and then ground with a
pestle. The powdered sample was then placed in a vial for
subsequent carbohydrate analysis using the NMR analytical
procedure.
Lignin Content
Klason lignin of control and treated samples were determined in
accordance with Tappi T-222 om-88, "Acid-insoluble lignin in wood
and pulp" (Tappi, 1994). Klason lignin was used to estimate of the
extent of delignification in the untreated and fungal-treated
chips. The Klason lignin method involves the hydrolysis and
solubilization of the carbohydrate component of the lignified
material, leaving the lignin as a residue, which is determined
gravimetrically. The acid soluble lignin procedure in wood
supplements the determination of acid-insoluble lignin. The soluble
fraction was determined in accordance with the useful method UM
250, "Acid-soluble lignin in wood and pulp" (Tappi, 1994). The sum
of the acid-insoluble lignin and of the acid-soluble lignin
represents the total lignin content in a sample. The wood in this
research project was not pre-extracted to remove extractives as is
typically done and recommended. The pre-extraction would have
removed a portion of the total mass from both the original wood
sample and the final extracted wood samples.
Carbohydrate Analysis
A new method has been developed involving .sup.1H-NMR analysis at
600 MHz at Analytical and Technical Services at ESF (Kiemle, 2001).
The procedure involves hydrolyzing the samples in an acid solution,
isolating the sugar monomers, and quantifying the individual
sugars. The NMR procedure is relatively fast when compared to other
carbohydrate analysis procedures. Samples were observable in the
range of 4.4-9.0 (ppm) chemical shifts.
A known amount of rhamnose was added to check the recovery of the
sugars and to verify the testing procedure. Rhamnose is a
monosaccharide that is not found in appreciable quantities in most
wood hydrolyzate, which gives distinct and well resolved signals
associated with the respective .alpha. and .beta. anomeric proton
doublets (.alpha. signal at 5.10 ppm and .beta. at 4.86 ppm). Prior
analysis of willow showed that rhamnose is present only in trace
quantities (Kiemle, 2001).
In making up the D.sub.2O solution, 0.5025 g (0.4459 g OD) of
rhamnose (MC 88.74%) was added to a 100 g sample of D.sub.2O. This
was carefully measured out in this way to ensure that 27.14 mg
(24.08 mg OD) of rhamnose would be in each 5.4 mL of D.sub.2O that
was then added to the dispersion in the procedure described below.
When exactly 1 ml of the total 6.02 ml solution was drawn, it would
contain 4 mg OD of rhamnose.
Oven-dried wood samples were ground in a Wiley Mill fitted with a
20-mesh screen. Using a vacuum oven, each sample was dried
overnight immediately prior to processing to remove any moisture it
may have absorbed between the time it was ground and processed. For
the extractant, the oven dried solids portion of the evaporated
extractant was determined after grinding with a mortar and
pestal.
For NMR analysis, 0.040 g of dried wood (or extracted solids) was
placed in a 15-ml thick-walled pressure tube with a teflon stopper
with 0.2 ml of 72% H.sub.2SO.sub.4. The dried wood dispersion is
stirred and allowed to digest at 40.degree. C. for 1.5 hours,
stirring every 15 minutes. Based on preliminary testing in this
study, only 15 minutes was found to be required for the hydrolysis
step for the ground and dried solids portion of the extract.
After the first digestion period, 5.4 ml of the D.sub.2O solution
(with rhamnose) was added to the vial. The vial was then placed in
an oven at 121.degree. C. for an additional hour. The rhamnose was
added with a portion of the D.sub.2O (NMR solvent) following the
last digestion step to ensure the rhamnose was not overly
degraded.
After cooling the suspension to approximately 30.degree. C., 0.4-mL
of 96.6% H.sub.2SO.sub.4 was added. The developers of the NMR
analysis method recommended the addition of the 96.6%
H.sub.2SO.sub.4 because the lowered pH of the acidic hydrolysis
medium effectively shifts the water NMR peak away from the region
of C-1 anomeric protons. This step avoids the possibility of having
the water interfere with the '1H signals resulting from the sugars.
(Kiemle, 2001) One ml of the hydrolyzate was then transferred to a
178-mm length NMR tube for analysis. Samples were analyzed using a
Bruker AVANCE 600 Mhz NMR system with the following specifications:
proton frequency: 600.13 MHz, broadband observe probe type (=),
(BBO): 30.degree. C., 90.degree. Pulse=11 .mu.sec, recycle time: 10
sec, acquisition time: 2.73 sec, sweep width: 10 ppm, center of
spectrum: 4.5 ppm, reference: acetone at 2.2 ppm. The signal
intensity of the NMR resonance is directly proportional to the
number of nuclei present. The response factor, the signal per mole
of material, is identical for all nuclei, in all molecular
environments, and is equal to unity (Kolbert, 2002).
The .sup.1H-NMR spectra recorded at 600 MHz from the 5 sugars and
the internal standard are given in FIG. 8 for the anomeric (C-1)
region of the spectrum (4.4-9.0 ppm). The total concentration of
each sugar is determined by summing up the total integrated area
from its respective .alpha. and .beta. anomeric proton doublets
(the .alpha. doublet occurs above 5.00 ppm and the .beta. doublet
occurs below 4.95 ppm.).
Results
During the biopulping procedure, a change in the wood chip color
was indicative of a successful treatment C. subvermispora produces
a characteristic color change upon successful colonization of the
wood after five to seven days of incubation. In addition, a white
fungal film covering the chips after two weeks is indicative of a
successful treatment. Unsuccessful treatments are missing the
characteristic color change and often colonies of other organisms
(such as Aspirgillus) are often seen. After 2 weeks of incubation
with C. subvermispora about half of the treated willow chips
appeared to have white fungal films incorporated throughout the
chips. These results were in contrast to the very repeatable growth
found for commercial wood chips in this apparatus. This was the
first study where a large amount of bark was included with the wood
chips in the reactor and further study of bark containing chips is
suggested to determine if that is the cause of this variability.
Only the successful treatments based on these visual criteria
(i.e., A, B, G, and H) are further analyzed for their effect on
xylan extraction.
The presence of the bark may have introduced variability into the
process. Tests carefully comparing samples with and without bark
removed would be useful. Future work could also include increasing
the amount of inoculum applied to the chips when bark is present as
more inoculum may be a simple way to overcome the higher potential
contamination in bark containing samples.
In this work, the willow source was from a single harvest of the
mixed willow clones, and the variability in Klason lignin in this
sample was modest compared to reported values from other
researchers who examined willow from various sources and harvest
times (Deka et al, 1992). Although C. subvermispora has been proven
to be a lignin degrader in prior works, the relatively short
two-week treatment used in this work was not sufficient to
reproducibly reduce the lignin content of the biomass willow chips.
Very little degradation of the lignin occurred in the biomass as a
result of fungal pretreatment. For example, based on the original
content of wood, Pretreatment G contained 28.2%.+-.0.9, prior to
pretreatment, and 28.5%.+-.0.6 following pretreatment. Pretreatment
H contained 28.2%.+-.0.9 prior to pretreatment, and 27.6%.+-.0.6
following pretreatment.
FIG. 9 shows the amount of lignin remaining in the wood following
the extraction based on the mass of the original wood. Although the
biotreatment did not appear to remove the lignin directly, the
lignin was degraded enough that an additional amount was almost
always removed from the biomass by the extraction procedure. The
results shown could be significant when considering the potential
cost savings associated with reduced chemical charge in the
digester and later in the bleach plant where chemicals are applied
to break down lignin and also to brighten the residual lignin.
However, this lignin comes out with the sugars in the extract and
may result in additional costs for processing the extract.
Table 1 shows the results for the soluble lignin in the liquid
extractant. A small portion of the lignin may have been washed away
in the chip washing step following the extraction and is not
captured in this analysis. The Tappi acid soluble test method
mainly estimates the degradation products from lignin. The results
in Table 1 may be looked at as a relative indication of the lignin
content of the extract, but should be interpreted with caution as
the very large dilutions necessary (over 900 times) would magnify
small sample errors. It should be noted that work by Jaffe (1974)
indicated that a similar hot water extraction procedure on birch
extracted 5% to 30% by weight of lignin. The results in Table 1 are
consistent with those of Jaffe (1974).
TABLE-US-00008 TABLE 1 Sample Temp. Pretreat Pretreat Pretreat
Pretreat H .degree. C. Pretreat A B G H (Duplication) Control 140
16.40% 12.30% no data no data no data 8.20% 145 17.20% 14.70%
11.00% no data no data 13.00% 150 17.60% 20.80% 15.40% 11.60%
12.30% 18.00% 155 18.60% no data 16.00% 14.20% 15.60% 16.20% 160 no
data no data no data no data no data 14.50%
In order for the pretreatment to be useful, it was important to
ensure the fungus was not consuming a significant amount of
cellulose. Cellulose is the dominant source of glucose in
hardwoods, and glucose content is used to estimate cellulose losses
in this study. FIG. 10 shows that the glucose content was similar
for the control and pretreated chips after extraction. The results
are promising, as the treatment did not lead to significant glucose
losses. This could serve as an indicator that the cellulose
component has been preserved. However, preservation of the glucose
does not necessarily mean that strength properties of the resulting
paper have been preserved. It is possible that the cellulose chains
have been weakened by internal cleavage without glucose losses.
FIG. 11 shows that maximum xylan recovery (measured as the monomer
sugar xylose) was 60.5% of the original xylose in the wood. This
was achieved with fungal pretreatment A at 150.degree. C. The
average recovery for all of the pretreatment trials at this
temperature was 37.4% with a range from 24.6% to 60.5% based on the
original xylose content in wood. All values were higher than the
23.2% recovery of the control untreated samples at 150.degree. C.
At temperatures between 140 and 150.degree. C., the treated wood
chips yielded equal or greater extraction amounts compared to
control chips at temperatures 5 to 10.degree. C. lower. The mass
loss in the chip wash following the extraction was 6.4% with the
pretreated samples, but only 1.3% with the control. Potentially,
additional xylose could be recovered from the wash water,
increasing the overall yield of the xylose.
The mass that was washed away was not collected, and therefore was
calculated by difference. However, if this mass had not been washed
away and the chips were left to dry with no washing, the washed
away mass would have remained in the wood and gone forward in the
process. These washed away materials were loosely bound to the
fibers based on the simple lab washing conducted in this study. On
a mill scale, these extractives could be recovered with a chip
washing step and then would not remain with the wood. As the
content of the extracts studied has little or negative value in
pulping, the washing to recover additional xylan and remove it from
the pulping stage is worth studying.
Conclusions
C. subvermispora pretreated wood chips allowed for the extraction
of more xylan from the wood or the use of a lower extraction
temperature than for control chips at a given extraction amount.
Recovered extracted xylan (measured as xylose) from the pretreated
chips at 150.degree. C. ranged from 24.6% to 60.5% based on the
original xylose content in wood. Hot water extraction without
fungal pretreatment at the same temperature and conditions, allowed
for the recovery of 23.1% of the xylose component. Future work is
needed to optimize the combination temperatures and extraction
times with respect to the xylan recovery. In addition, the recovery
of the post-extraction chip washing liquor may yield additional
xylan recovery from biomass willow chips.
The lignin remaining with the wood after water extraction was lower
for the pretreated samples than for the untreated wood chips. This
might well result in savings later in the process when lignin is to
be removed or brightened during pulping. More work should be done
to ascertain the relative effects of fungal pretreatment and pH on
the lignin removal during the water extraction process. The effect
of the hemicellulose extraction and the concurrent lignin
modification on the subsequent pulping process is yet to be
explored.
The glucose component in the extracted wood chips did not change
between pretreated and untreated chips. This indicates that the
cellulose content has not been measurably affected by the
pretreatment. However, this does not necessarily mean that strength
properties of the resulting paper have been preserved and it yet to
be determined. Past results have shown biopulping preserved the
strength properties of the chips, but this should be explored
further for this particular post-biotreatment extraction
procedure.
EXAMPLE 4
A typical bleaching sequence for hardwood kraft pulps is
OD.sub.0EopD.sub.1, or OD.sub.0EopD.sub.1P. Softwood kraft pulps
normally require more chlorine dioxide (ClO.sub.2) and a typical
sequence is OD.sub.0EopD.sub.1ED.sub.2. Alkaline O.sub.2 is
represented by O while D.sub.0=ClO.sub.2 delignification at end pH
2-3; E=alkaline extraction with NaOH (Ep when hydrogen peroxide is
added and Eop when O.sub.2 and H.sub.2O.sub.2 are added for
incremental delignification; D.sub.1=ClO.sub.2 brightening at end
pH 3.5-4.5; D.sub.2=ClO.sub.2 brightening at end pH 4-6; and
P=H.sub.2O.sub.2 brightening at pH>10.
The addition of O.sub.2 addition to D stages has not been
investigated. It is understood that carbon-centered free radicals
are generated in D or D/P.sub.M bleaching (P.sub.M=hydrogen
peroxide bleaching catalyzed by sodium molybdate). The P.sub.M is
added to a D stage without any change in its treatment
conditions.
Since O.sub.2 is cheaper than ClO.sub.2 it would be economically
beneficial if these carbon-centered free radicals are coupled with
O.sub.2 instead of the more expensive ClO.sub.2. Coupling with
O.sub.2 is shown in equation [1] below. The peroxy radical formed
can abstract a hydrogen atom from reactive lignin sites thus
affording more delignification (equation 2)
RH.sub.2C.+O.sub.2.fwdarw.RH.sub.2COO. [1]
RH.sub.2COO.+LH.fwdarw.L.+RH.sub.2COOH [2]
The peroxide generated in equation [2] could further degrade or
brighten the lignin. Unfortunately, the peroxide could also be
catalytically decomposed by transition metals (Eqn. [3) to form the
hydroxyl radical (.OH) that would depolymerized the carbohydrate
fraction.
RH.sub.2COOH+M.sup.n+.fwdarw.RH.sub.2CO.sup.-+.OH+M.sup.(n+1)+
[3]
Pursuant to these principles, a large batch of hardwood kraft pulp
was assembled to investigate O.sub.2 addition to D stages. All of
the available pulps that were already delignified with alkaline
O.sub.2 were collected. These pulps were dispersed in a large
plastic vessel at .about.5% consistency. The pulp mixture was then
treated with 1.12% KHSO.sub.5 (0.25% equiv. H.sub.2O.sub.2) at room
temperature overnight. The pH the following morning was .about.4.7.
The pulp was then treated with 0.2% Na.sub.5DTPA with
Na.sub.2CO.sub.3 being used to achieve pH.about.6. The pulp was
dewatered to .about.25% consistency the following day. This pulp
was the starting material for bleaching under D.sub.1 stage
conditions. It had a kappa number of 8.4, a viscosity of 23.0 cP
and a brightness of 62.5% Elrepho. The pulp contained 4 ppm Mn, 25
ppm Fe and 7 ppm Cu.
Most of the bleaching experiments were performed in duplicate and
never were duplicate trials performed on the same day. The first
results are outlined in trial numbers 1a-2b in Table 1. All of the
chemistry that was projected was observed in the data. Oxygen
addition resulted in a higher brightness and a lower viscosity
(used to estimate the degree of polymerization (DP) of the
cellulose). Although the brightness differences caused by O.sub.2
addition to a D.sub.1 stage were quite significant O.sub.2 addition
to D/P.sub.M bleaching was investigated as confirmation. Those
results are summarized in trial numbers 3a to 4b (Table 1). It can
be seen that O.sub.2 addition resulted in an .about.1.5 point
brightness increase.
Experimentation was conducted to address the lower viscosity
associated with O.sub.2 addition. It is known that magnesium
cations improve viscosity and increases brightness in alkaline
O.sub.2 delignification. One of the most credible explanations of
this phenomenon is that Mg cations disrupt the free radical
propagation mechanism by forming complexes with superoxide anions
(.OO.sup.-). When NaOH was replaced by Mg(OH).sub.2 there were
significant improvements in both brightness and viscosity (trials 5
and 6). On a weight basis, Mg(OH).sub.2 presently costs only
one-half that of NaOH. Therefore, by replacing NaOH with
Mg(OH).sub.2 and adding O.sub.2 one can achieve .about.3.5 points
higher brightness and lower bleaching cost. The cost of O.sub.2
addition would be negligible.
Next, O.sub.2 addition under D.sub.0 condition with a 13 kappa
number unbleached hardwood pulp was investigated. There was a
significant increase in brightness after D.sub.0Ep but AOX in the
D.sub.0 effluent was only decreased by 4.5% (Table 2).
TABLE-US-00009 TABLE 1 Simultaneous Bleaching with ClO.sub.2 and
O.sub.2 O.sub.2 End Bright. % Viscosity Trial # % ClO.sub.2 %
H.sub.2O.sub.2 % NaOH Addition.sup.1 pH Elrepho Kappa # cP 1a 1.0 0
0.5 N 3.5 77.2 2.7 20.5 1b 1.0 0 0.5 N 3.4 76.2 2.7 19.5 2a 1.0 0
0.5 Y 3.4 78.6 2.4 18.1 2b 1.0 0 0.5 Y 3.3 78.0 2.4 18.0 3a 0.6 0.4
0.3 N 4.5 72.6 -- -- 3b 0.6 0.4 0.3 N 4.1 72.8 -- -- 4a 0.6 0.4 0.3
Y 3.8 74.7 -- -- 4b 0.6 0.4 0.3 Y 3.8 73.9 -- -- 5 1.0 0 0.36% Y
3.3 79.9 2.4 21.8 Mg(OH).sub.2 6 1.0 0 0.40% Y 3.6 80.4 2.4 20.5
Mg(OH).sub.2 .sup.1O.sub.2 partial pressure = 0.72 MPa
TABLE-US-00010 TABLE 2 Addition of Oxygen to a Stage D.sub.0 With
N.sub.2 With O.sub.2 Unbleached Kappa No. 13.0.sup.1 13.0.sup.1
D.sub.0 Stage End pH 3.1 3.2 AOX in D.sub.0 effluent.sup.2 0.45
0.43 Brightness after D.sub.0 stage.sup.3 54.2 58.6 Brightness
after Ep Stage.sup.3 63.8 65.2 Kappa No. after Ep Stage 4.7 4.4
.sup.1Kraft pulp produced from a mixture of sugar maple, white
birch and cottonwood (1:1:1) by Econotech Lab, British Columbia,
Canada .sup.2Determined by Andritz Inc., Glens Falls, NY; values in
g/kg pulp or kg/ton pulp .sup.3% Elrepho
The next step was the investigation of a mill pulp with low kappa
number after ODEop treatment. An eucalyptus kraft pulp with kappa
number 2.0 and 68% Elrepho brightness was obtained. This pulp was
first bleached with 0.8% ClO.sub.2 and 0.30% Mg(OH).sub.2. A
brightness of 87.6% was obtained but the end pH was 7.0. The
experiment was repeated but the Mg(OH).sub.2 dose was decreased to
0.15%. A brightness of 87.4% and end pH 6.6 were obtained.
Approximately 7 months later neither pulp had lost any brightness
whatsoever as a result of thermal reversion. Both pulps were stored
at .about.30% consistency and at room temperature (20-25.degree.
C.) in a laboratory. Eucalyptus kraft pulps generally reverted more
than other wood species and sometimes this reversion can be severe.
The initial and reverted brightnesses of these pulps are presented
in Table 3.
TABLE-US-00011 TABLE 3 Initial and Reverted Brightness of
Eucalyptus Kraft Pulp bleached with ClO.sub.2/Mg(OH).sub.2/O.sub.2
Sam- Bleached Reverted ple ClO.sub.2 % Mg(OH).sub.2 % End pH
Brightness.sup.1 Brightness.sup.1 1 0.8 0.3 7.0 87.6 87.8 (Sep. 20,
2005) Apr. 12, 2006 2 0.8 0.15 6.6 87.4 87.3 (Sep. 21, 2005) Apr.
12, 2006 .sup.1% Elrepho
Finally, a large batch of a softwood kraft pulp from loblolly pine
(Pinus taeda) was delignified by OQP to kappa number 6.8 and 59.2%
ISO brightness and shipped to an independent laboratory for
confirmation. The agreed up NaOH and Mg(OH).sub.2 doses were too
high and an end pH of 7.2 was obtained for ClO.sub.2/NaOH/N.sub.2
while the value was 7.6 for ClO.sub.2/Mg(OH).sub.2/O.sub.2. The
comparison was repeated by the independent laboratory with less
NaOH and Mg(OH).sub.2. All the results are documented in Table 4.
These results show a one point brightness improvement for
ClO.sub.2/Mg(OH).sub.2/O.sub.2 at both pH.about.7.5 and
pH.about.4.5. The independent laboratory performed accelerated
thermal reversion for the pH.about.4.5 samples and saw no
improvement for ClO.sub.2/Mg(OH).sub.2/O.sub.2. However, the
pH.about.7.5 samples were returned and the brightness determination
showed that the NaOH/N.sub.2 sample was reverting at a much faster
rate than the ClO.sub.2/Mg(OH).sub.2/O.sub.2 sample. The
independent laboratory results was consistent with those in Table 3
that show no decrease in brightening efficiency as the end pH for
ClO.sub.2/Mg(OH).sub.2/O.sub.2 is increased above the reported
optimum of .about.4.0. Therefore, by using
ClO.sub.2/Mg(OH).sub.2/O.sub.2 at pH.gtoreq.7 excellent bleaching
is obtained and reversion is minimal.
TABLE-US-00012 TABLE 4 Oxygen and Mg(OH).sub.2 Addition to D.sub.1
Stage bleaching of Loblolly Pine Kraft Pulp with kappa number 6.8
and 59.2% ISO Brightness Kappa Number 6.8 Viscosity (mPa s) 9.8
Brightness, % ISO 59.2 D Stage: 70.degree. C. 120 min., 10% cons.
Control Control ClO.sub.2, %.sup.1 1.0 1.0 1.0 1.0 NaOH, %.sup.1
0.5 -- 0.2 -- Mg(OH).sub.2, %.sup.1 -- 0.43 -- 0.25 Oxygen
pressure, psi -- 80 -- 80 Final pH 7.2 7.6 4.2 4.7 ClO.sub.2
Consumed, % 0.77 0.90 1.0 1.0 ISO Brightness, % 79.4 80.3 79.3 80.3
Reverted Brightness units ~2.0 ~0 2.2 2.1 4 hr, @ 105 C. .sup.1% on
pulp
EXAMPLE 5
Raw Material
Acer saccharum (Sugar Maple) wood logs obtained from ESF Forest
Properties were debarked and chipped in a Carthage chipper located
in the Paper Science and Engineering department at SUNY-ESF to a
size normally used in industry (2.5.times.2.0.times.0.5 cm). The
chips were air dried to moisture content of 10-12% and stored in a
single lot for use in all the experimental work in order to avoid
differences in composition. One part of these sugar maple chips was
ground in a Wiley Mill to a particle size passing a 30-mesh screen.
The wood meal obtained was stored separately in a single lot to be
used in the autohydrolysis experiments on wood meal.
Analysis of Wood
Sugars analysis of both the raw wood and the extracted wood samples
was performed by .sup.1H-NMR spectroscopy with the Bruker AVANCE
600 MHz NMR system using a method described by Copur et al. 2002.
Extracted wood chips were ground to a particle size <30-mesh
screen using a Wiley Mill. For NMR analysis, 0.20 ml of 72%
H.sub.2SO.sub.4 was added to 0.040 g of OD (oven dried) milled wood
mass. After stirring, the dispersion was allowed to digest at
40.degree. C. for 60 min. in a water bath with additional stirring
every 15 minutes. After this digestion, 5.4 ml of D.sub.2O (NMR
solvent) was added to the dispersion, which was then autoclaved at
121.degree. C. for 60 min. After cooling 0.42 ml of 96%
H.sub.2SO.sub.4 was added which was followed by the addition of TMA
(tri-methyl amine), an internal standard. Klason lignin and acid
soluble lignin were determined by standard TAPPI methods, T 222
om-88 and UM 250, respectively.
Hydrothermal Treatment of Wood Samples
To obtain the desired liquor to solid ratio (LSR) in the
autohydrolysis experiments, wood chips or wood meal were mixed with
water and the moisture content of the raw material (sugar maple
wood chips or wood meal) was considered as water in the material
balances. The wood meal was treated in 100-ml stainless steel
reaction bombs, which were heated to the desired temperature by
placing them in a Techne (Tempunit.RTM. TU-16) oil bath, that had
been preheated to the desired temperature, and controlled within
.+-.1.degree. C. The reaction bombs were filled up to 75% of the
total volume to provide space for liquid expansion at the reaction
temperature. Wood chips were treated in a 4-liter M/K digester
equipped with a centrifugal pump for liquor circulation and a PID
temperature controller. The time to heat wood chips to the desired
temperature in M/K digester was about 25-30 minutes. For wood meal,
since stainless steel is a good conductor of heat, the time to
reach the reaction temperature in the reaction bomb was assumed to
be 5 minutes. Since a portion of the reaction material may have
reacted during the heating period, only data corresponding to the
isothermal reaction condition were used in the data analysis. For
both wood meal and wood chips, time zero was taken to be the
beginning of the isothermal stage. For wood meal the reaction was
terminated by quenching the reaction bombs in cold water and for
wood chips by switching off the M/K digester and discharging the
liquor through a heat exchanger.
Analysis of Hydrolyzate from Hydrothermal Treatment
For quantification of sugars and sugar degraded products i.e.
furfural and HMF in the hydrolyzate obtained from the
autohydrolysis experiments, analysis was performed on two aliquots.
The first aliquot was used directly for the determination of
furfural and HMF with .sup.1H-NMR, whereas for determining sugars,
0.24 ml of 96% H.sub.2SO.sub.4 was added to 1.0 g of the second
aliquot of the liquid hydrolyzate which was then heated at
80.degree. C. for 60 min in a water bath. The digested sample was
tested for quantification of the sugars with .sup.1H-NMR. In both
aliquots, TMA was used as an internal standard for the reference
peak.
Treatment of Wood by Severity Analysis
To evaluate the hemicellulose hydrolysis process, the severity
approach was utilized. The severity analysis is based on the
assumption that the overall kinetics follow a first-order
concentration dependence and the rate constants have the
Arrhenius-type dependence on temperature. However, in this approach
time and temperature are combined into a single factor called the
severity factor (Overend and Chornet, 1987). Due to its simplified
form and more general application (on different raw materials) we
have interpreted our data using the severity analysis approach. The
model for hemicellulose hydrolysis as presented by Garrote et al.,
2002 is given by
C.sub.A=(1-.alpha.).times.C.sub.A0+.alpha..times.C.sub.A0.times.exp(-k.su-
b.r.times.R.sub.o) (1) where C.sub.A is the concentration of the
reactant at time, t, C.sub.A0 that at time, t=0, .alpha. is the
weight fraction of susceptible xylan in the raw material
(0<.alpha.<1), k.sub.r is the kinetic constant measured at a
reference temperature T.sub.r and R.sub.o is the severity factor
which is defined as
.intg..function..times..omega..times..times.d ##EQU00001## where T
is the absolute temperature while .omega. is a function of the
reference temperature T.sub.r and activation energy, E.sub..alpha.
and is defined as
.omega..times. ##EQU00002##
Since time and temperature are combined in a single parameter i.e.
the severity factor, the main advantage of severity analysis is
that it enables one to compare the severity of the hydrolysis
treatment for a wide range of operation conditions (time and
temperature) represented by a single reaction ordinate (R.sub.o).
To study the optimum conditions for xylose yield in the
hydrolyzate, the experiments were conducted for different times and
temperature conditions in order to vary the single variable
(R.sub.o) from a region of low severity (log R.sub.o=2) where
fractionation or hemicellulose hydrolysis begins to the region of
high severity (log R.sub.o>3.0) where depolymerization,
condensation and degradation reactions start to occur (Heitz et
al., 1991; Zhuang and Vidal, 1996). Equation (2) was used to
calculate the severity factor at the reference temperature
T.sub.r=145.degree. C. According to the previous studies (Belkacemi
et al., 1991; Abatzoglou et al., 1992; Garrote et al., 2002) the
selection of the reference temperature T.sub.r is not influential
for data analysis and most of the authors (Overend and Chornet,
1987; Heitz et al., 1991; Zhuang and Vidal, 1996) have chosen
T.sub.r=145.degree. C., as the reference temperature. We also
selected T.sub.r=145.degree. C. in our study because at this
temperature we observed minimum or negligible hemicellolose
solubilization at short reaction times. The relation between the
treatment severity and experimental variables (time and
temperature) for the experiments conducted in this study is shown
in Table 1.
TABLE-US-00013 TABLE 1 Experimental conditions of time and
temperature and their relation to the severity factor (see Table 3
for values of E.sub..alpha. used to calculate .omega.) Experimental
variables Severity factor (R.sub.o) Temperature (.degree. C.) Time
(min.) log (R.sub.o) (R.sub.o is in min.) 160 120 2.6 160 180 2.8
160 240 2.9 175 90 3.0 175 120 3.1
Material Balances
The material balance is important for determining the conversion
efficiency of a chemical process and it also provides the
appropriateness of the experimental conditions applied in the
process. The results of the material balances for the selected
experiments that cover the range of treatment severity are given in
Table 2.
TABLE-US-00014 TABLE 2 Material balances in the experiments
conducted at different treatment severities Yield of water Yield of
water- log (R.sub.o) insoluble fraction soluble fraction Material
losses* (R.sub.o is in min.) (wt %) (wt %) (wt %) 2.6 79.0 16.8 4.2
2.8 76.1 19.9 4.0 2.9 76.2 19.2 4.6 3.0 76.9 18.1 5.0 3.1 75.1 16.2
8.6 *by difference
In autohydrolysis of sugar maple wood, the yield of the water
insoluble fraction decreased with the increased treatment severity
(Table 2). 24.9% of the initial wood mass could be solubilized at
the reaction severity of log R.sub.o=3.1. The yield of water
soluble fraction also increased with increasing treatment severity
and after reaching a maximum recovery of 19.9% of initial wood mass
in the hydrolyzate at log R.sub.o=2.8, it decreased. The possible
explanation of this phenomenon is that at higher treatment
severities, acidic conditions prevail in the solution (at log
R.sub.o=3.1, pH=2.8 which lead to various condensation and
degradation reactions via which degraded products like furfural,
HMF, levulinic acid, formic acid and other volatile or unidentified
compounds are formed (Sjostorm, 1993). This is also evident from
the material balance closure presented in Table 2, which shows that
as the treatment severity increased, the amount of lost mass also
increased.
Severity Analysis of Hemicellulose Solubilization and
Deacetylation
The severity approach has been used to fit the residual xylan data
by various authors for different raw materials under various time
and temperature conditions (i.e. data obtained for isothermal and
non-isothermal temperature conditions and different liquor to
solids ratios). In this work, data for hemicellulose solubilization
obtained during the isothermal conditions for sugar maple wood are
considered. C.sub.A is defined as the grams of unconverted
substance (xylan or acetyl groups) per 100 grams of the initial
substance. Equation (1) was fitted to the experimental data
obtained in this work and the values of the regression parameters
.alpha., k.sub.r, and E.sub..alpha. were calculated by minimization
of the sum of the squares of the deviation between the variable
C.sub.A/C.sub.A0 (see eq. (1)) and its experimental value. For
optimization, the SOLVER function of MS-EXCEL was used. The fitting
parameters obtained in this work are compared with the parameters
obtained by various authors, as given by Garrote et al., 2002, and
are shown in Tables 3 and 4 for xylan solubilization and
deacetylation, respectively. From Tables 3 and 4 it can be observed
that .alpha. (weight fraction of susceptible xylan) obtained in
this work for the wood meal data is in the range
(.alpha.=0.83-0.89) previously reported in the literature. It is
important to note that the value of .alpha. for wood chips is lower
compared to that for wood meal. This is explained by the reason
that due to the larger particle size of wood chips there is
diffusion limitation and at the comparable treatment severity less
amount of xylan solubilizes or in other words wood chips have less
weight fraction of susceptible xylan available than wood meal that
can be solubilized at the same level of treatment severity.
The activation energies, E.sub..alpha. determined for both xylan
solubilization and deacetylation for wood chips are higher compared
to the respective activation energies for wood meal (see Tables 3
and 4). The difference in the activation energy for wood chips and
wood meal can be justified by offering the same explanation of
diffusion limitation in wood chips. The values of activation
energies, E.sub..alpha. determined for both xylan solubilization
and deacetylation of wood chips and wood meal in this study are
well within the range (E.sub..alpha.=112-137 kJ mol.sup.-1) of
activation energies determined previously for various raw materials
(Tables 3 and 4). The comparison of experimental results and
theoretical predictions are presented in FIGS. 12 and 13 for xylan
solubilization and deacetylation, respectively for both wood meal
and wood chips.
TABLE-US-00015 TABLE 3 Values of regression parameters obtained for
xylan solubilization .alpha. (dimension- Source of Raw material
less) k.sub.r 10.sup.3 (min.sup.-1) E.sub.a (kJ mol.sup.-1) data
Sugar 0.780 7.00 122 this work Maple* Sugar 0.880 4.00 112 this
work Maple.sup..psi. Eucalyptus 0.857 6.44 124 Garrote et al.
globulus 2002 [9] Populus 0.826 2.25 137 [9] tremuloides Birch
0.889 5.28 135 [9] Corncobs 0.882 5.43 115 [9] *wood chips,
.sup..psi.wood meal
TABLE-US-00016 TABLE 4 Values of regression parameters obtained for
acetyl groups solubilization .alpha. (dimension- Source of Raw
material less) k.sub.r 10.sup.3 (min.sup.-1) E.sub.a (kJ
mol.sup.-1) data Sugar 0.750 3.00 115 this work Maple* Sugar 0.880
3.00 108 this work Maple.sup..psi. Hardwoods 0.879 6.02 121 Garrote
et al. Corncobs 0.899 6.05 111 2002 *wood chips, .sup..psi.wood
meal
From FIGS. 12 and 13 it can be seen that as the treatment severity
increases the extent of xylan solubilization or deacetylation
increases for both wood chips and wood meal and reaches a constant
residual amount of xylan in both wood chips and wood meal which is
difficult to hydrolyse. This residual xylan, which has been
reported in earlier studies (Conner, 1984; Conner and Lorenz, 1986)
as less-reactive xylan is considered to be in deep association with
cellulose and lignin and is difficult to hydrolyse with
hydrothermal treatment without affecting the cellulose and lignin.
From FIGS. 12 and 13 it can be observed that the experimental data
is in fair agreement with the model [eq. (1)]. As can be seen from
FIGS. 12 and 13 we did not have much data in the lower range of the
treatment severity since the experiments in this study were
conducted in the severity range of 2.0<=log R.sub.o<=3.1.
More experimental work is expected to be conducted at low treatment
severities.
Yields of Acetyl Groups, Xylose and Furfural in the Hydrolyzate
From FIG. 12 it can be concluded that as the extent of treatment
severity increases, xylan solubilization also increases and about
90% of the initial xylan hydrolysis is achieved at a treatment
severity of log R.sub.o=3.1. It has been reported (Heitz et al.,
1991) that the solubilized xylan exists initially as xylooligomers
and xylose in the extracted hydrolyzate. As soon as free acetyl
groups become available (due to the cleavage of acetyl groups
directly from the xylan chain or from xylooligomers present in the
hydrolyzate), it leads to the formation of acetic acid (Springer
and Harris, 1982; Heitz et al., 1991). The dissociation of the
acetic acid thus formed results in an increased concentration of
hydronium ions, which further catalyzes the autohydrolysis reaction
and results in a decrease in the xylooligomers concentration and an
increase in the xylose concentration in the hydrolyzate. The
concentration of the acetyl groups in the hydrolyzate with the
increased severity is shown in FIG. 14. It is interesting to note
that at severity of log R.sub.o=3.0, the concentration of acetyl
groups in the hydrolyzate is about 3 g/100 g of initial wood which
corresponds to 80% of the acetyl groups initially present in the
wood. An increase in the hydronium ions or a drop in pH with the
increased treatment severity is shown in FIG. 15.
The relationship between the concentration of xylose and treatment
severity is shown in FIG. 16. From FIG. 16 it can be noticed that
xylose concentration increases initially and the maximum amount of
xylose recovery of 65% as xylose, based on total initial xylan in
wood, in the hydrolyzate is obtained at log R.sub.o=2.8 which
corresponds to a 3-hr treatment of sugar maple chips at 160.degree.
C. (Table 1). The maximum amount of xylose recovered in the
hydrolyzate in our study is consistent with the range of maximum
pentosans (xylose in our study) recovery of 65-70% that has been
reported in earlier studies (Zhuang and Vidal, 1996). The reason
for the maximum xylose recovery in the hydrolyzate to be limited to
65-70% is due to competition between two simultaneous reactions
taking place in the process: (i) xylan solubilisation and (ii)
degradation of the solubilized xylan to furfural and other
degradation products (Zhuang and Vidal, 1996). It is important to
note in FIG. 16 that at severities beyond log R.sub.o>2.8,
xylose concentration in the hydrolyzate starts decreasing owing to
the formation of furfural and other degradation products of xylose.
FIG. 17 shows the formation of furfural with the increased
treatment severity. Up to a severity of log R.sub.o=2.5, no
considerable formation of furfural is observed but as the treatment
severity is increased above log R.sub.o>2.8, the concentration
of furfural reaches to a level of 1 g/100 g of initial wood.
The above embodiments and examples are given to illustrate the
scope and spirit of the present application. These embodiments and
examples will make apparent, to those skilled in the art, other
embodiments and examples. Those other embodiments and examples are
within the contemplation of the present invention. Therefore, the
present invention should be limited only by the appended
claims.
* * * * *